Chiral3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole derivatives and 5,5-dimethyl-3-[(1h-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihyddroisoxazole derivatives, method for the production thereof, and use of same as herbicides and plant growth regulators

ABSTRACT

The invention relates to 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole derivatives and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives of the formula (I) and their salts 
                         
processes for their preparation and their use as herbicides and plant growth regulators, in particular as herbicides for the selective control of harmful plants in crops of useful plants.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 USC 120 to 12/744,042 filed May 20, 2010 which is a §371 national stage application of PCT/EP2008/009438 filed Nov. 8, 2008, which claims priority to European Application 07023152.7 filed Nov. 30, 2007.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole derivatives and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives. The present invention furthermore provides mixtures of the isoxazole derivatives mentioned above with other herbicides and/or safeners. In addition, the present invention relates to processes for preparing the isoxazole derivatives mentioned above and to the use of these compounds as plant growth regulators alone and in mixtures with safeners and/or in mixtures with other herbicides, in particular to their use for controlling plants in specific plant crops or as crop protection regulators.

2. Description of Related Art

It is already known from the prior art that certain 5,5-dimethyl-4,5-dihydroisoxazole derivatives have herbicidal properties. Thus, the patents JP 1996/08225548 A and WO 2001/012613 A disclose herbicidally active 4,5-dihydroisoxazole derivatives which carry a benzylthio, benzylsulfinyl or benzylsulfonyl group as substituent at the 3-position of the isoxazoline ring.

WO 2002/062770 A (=EP-A-1 364 946), WO 2003/000686 A, WO 2006/024820 A, WO 2007/003294 A, WO 2007/071900 A, WO 2006/037945 A, WO 2005/104848 A and US 2005/256004 A1 describe various 3-[(pyrazolylmethyl)thio], 3-[(pyrazolylmethyl)sulfinyl] and 3-[(pyrazolylmethyl)sulfonyl]-4,5-dihydroisoxazole derivatives, their preparation and their use as herbicides.

Furthermore, WO 2004/013106 A and WO 2007/003295 A describe processes for preparing corresponding isoxazole derivatives.

However, on application, the active compounds already known from the prior art have disadvantages, be it

-   (a) that they have no or else insufficient herbicidal activity     against harmful plants, -   (b) that the spectrum of harmful plants that can be controlled with     one active compound is not wide enough, and/or -   (c) that their selectivity in crops of useful plants is     insufficient.

In particular, the herbicidally active isoxazole compounds known from the prior art have unsatisfactory herbicidal activity against specific weed grasses and at the same time unsatisfactory crop compatibility in specific crops.

SUMMARY OF THE INVENTION

It is therefore desirable to provide alternative chemical active compounds based on isoxazole derivatives which can be used as herbicides or plant growth regulators and which are associated with certain advantages compared to systems known from the prior art.

It is thus the general object of the present invention to provide alternative isoxazole derivatives which can be used as herbicides or plant growth regulators, in particular having a satisfactory herbicidal action against harmful plants, covering a broad spectrum of harmful plants and/or having high selectivity in crops of useful plants. Preferably, these isoxazole derivatives should have a better property profile, in particular better herbicidal activity against harmful plants, cover a broader spectrum of harmful plants and/or have higher selectivity in crops of useful plants than the isoxazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active isoxazole compounds having improved herbicidal activity against specific weed grasses compared to isoxazole derivatives known from the prior art.

Another particular object of the present invention is to provide herbicidally active isoxazole compounds having improved crop compatibility in specific crops compared to isoxazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active isoxazole compounds which, at the same time, have improved herbicidal activity against specific weed grasses and improved crop compatibility in specific crops compared to isoxazole derivatives known from the prior art.

The present invention now provides specific 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives optically active at the sulfoxide function, which compounds have advantages compared to the compounds known from the prior art or racemic mixtures thereof.

According to the invention, it has been found that these 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives according to the invention and which are optically active at the sulfoxide function have improved herbicidal activity against Alopecurus myosuroides (black-grass), Lolium multiflorum (Italian ryegrass) and Setaria viridis (green foxtail) compared to isoxazole derivatives known from the prior art.

According to the invention, it has furthermore been found that these 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives according to the invention and which are optically active at the sulfoxide function, have improved crop compatibility in Brassica napus (winter rape) compared to isoxazole derivatives known from the prior art.

According to the invention, it has finally also been found that these 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives according to the invention and which are optically active at the sulfoxide function, have both improved herbicidal activity against Alopecurus myosuroides (black-grass), Lolium multiflorum (Italian ryegrass) and Setaria viridis (green foxtail) and improved crop compatibility in Brassica napus (winter rape) compared to isoxazole derivatives known from the prior art.

Accordingly, the present invention provides optically active compounds of the formula (I), their agrochemically acceptable salts and their agrochemically acceptable quaternized nitrogen derivatives

in which

Y is either

and

the individual substituents R¹ to R⁸ are each independently of one another selected from the group consisting of

-   -   hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH,         formyl,     -   (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl,         (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy,         (C₁-C₆)-haloalkylcarbonyloxy,         (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl,         (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-alkyl,         (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl,         (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl,     -   (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkoxycarbonyl,         (C₁-C₆)-haloalkoxycarbonyl,         (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl,         (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl,         (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl,         (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl,     -   (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkenylcarbonyl,         (C₂-C₆)-haloalkenylcarbonyl, (C₂-C₆)-alkenyloxy,         (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-alkenyloxycarbonyl,         (C₂-C₆)-haloalkenyloxycarbonyl,     -   (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₂-C₆)-alkynylcarbonyl,         (C₂-C₆)-haloalkynylcarbonyl, (C₂-C₆)-alkynyloxy,         (C₂-C₆)-haloalkynyloxy, (C₂-C₆)-alkynyloxy-carbonyl,         (C₂-C₆)-haloalkynyloxycarbonyl,     -   (C₁-C₆)-alkylthiocarbonyl, (C₁-C₆)-haloalkylthiocarbonyl,         (C₁-C₆)-alkylthiocarbonyloxy, (C₁-C₆)-haloalkylthiocarbonyloxy,     -   (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy,         (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyl,         (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy,     -   (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl,         (C₆-C₁₄)-aryloxycarbonyl,     -   (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl,         (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy,         (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyl,         (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyloxy,         (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyl,         (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy,     -   (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl,         (C₁-C₆)-haloalkylsulfonyl, (C₁-C₆)-haloalkylthio,         (C₁-C₆)-haloalkylsulfinyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl,         (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl,         (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl,         (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-alkyl,         (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl,         (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-alkyl,         (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl,         (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl,         (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl,         (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl,         (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl,         (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl,         (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkylsulfonyloxy,     -   (C₄-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio, (C₆-C₁₄)-arylsulfinyl,     -   mono-((C₁-C₆)-alkyl)-amino, mono-((C₁-C₆)-haloalkyl)-amino,         di-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-haloalkyl)-amino,         ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)-amino,         N—((C₁-C₆)-alkanoyl)-amino, N—((C₁-C₆)-haloalkanoyl)-amino,         aminocarbonyl-(C₁-C₆)-alkyl,         mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,         mono-((C₁-C₆)-alkyl)-aminocarbonyl,         di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,     -   (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy,         (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy,     -   (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy,         (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl,         (C₃-C₈)-cycloalkylcarbonyloxy, (C₃-C₈)-cycloalkoxycarbonyloxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy,         (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyloxy,     -   (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy,         (C₃-C₈)-cycloalkenylcarbonyl, (C₃-C₈)-cycloalkenyloxycarbonyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyl,         (C₃-C₈)-cycloalkenylcarbonyloxy,         (C₃-C₈)-cycloalkenyloxycarbonyloxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy,         (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy,     -   (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio,         (C₃-C₈)-cycloalkenylthio, (C₃-C₆)-alkynylthio,     -   hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy,         cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl,     -   3-oxetanyloxy,     -   pyrimidinyl-2-yl and 4,6-dimethoxypyrimidinyl-2-yl,     -   C(O)NR⁹R¹⁰ where R⁹ and R¹⁰ independently of one another are         hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl,         or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which         may contain one oxygen or sulfur atom or one or two amino or         (C₁-C₆)-alkylamino groups,     -   where the radicals mentioned may, if appropriate, be attached         cyclically to one another, provided they are ortho to one         another

-   and/or     -   two substituents ortho to one another together form a         (C₁-C₆)-alkylene group which may contain one or more oxygen         and/or sulfur atoms, where the (C₁-C₆)-alkylene group may be         mono- or polysubstituted by halogen and the halogen substituents         in question may be identical or different; and         where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

If the radicals comprising cycloalkyl and aryl are substituted, the substituents are preferably selected from the group consisting of (C₁-C₆)-alkyl, (C₁-C₅)-haloalkyl, (C₁-C₆)-alkoxy, nitro, cyano, (C₁-C₃)-cycloalkyl, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl or halogen, where the radicals mentioned may, if appropriate, be cyclically attached to one another, provided they are ortho to each other.

In the first instance, preferred, particularly preferred and very particularly preferred meanings of the individual substituents R¹ to R⁸ are described below.

A first embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R¹ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy,     (C₃-C₆)-cycloalkoxycarbonyl, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy,     (C₃-C₆)-cycloalkoxy, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy,     (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-haloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy,     di-(C₁-C₄)-alkylamino, C₆-aryl-(C₁-C₄)-alkyl,     (C₃-C₄)-alkenyloxycarbonyl, (C₂-C₄)-alkynyloxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxy, formyl,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, phenyl; —C(O)NR⁹R¹⁰, where R⁹ and     R¹⁰ independently of one another are selected from the group     consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a     (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom     or one or two amino or (C₁-C₆)-alkylamino groups; or R¹ together     with R² forms a radical —OCH₂CH₂O—, —OCF₂O— or —OCH₂OCH₂—,     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R¹ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, OH, NH₂, NO₂, Me, Et, Ph, CHF₂, CF₃, OMe, OEt,     OPr, OiPr, OBu, OcPen, OcHex, OCHF₂, OCF₃, OCH₂CF₃, C(O)OH, C(O)OMe,     C(O)OEt, C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OcPen,     C(O)OCH₂CH═CH₂, C(O)OCH₂C≡CH, C(O)OCH₂Ph, CH₂OMe, CH₂OEt, CH₂OBu,     OCH₂cPr, OCH₂CH═CH₂, OCH₂C≡CH, OCH₂Ph, OCH₂C(O)OMe, OCH₂C(O)OEt,     OCH₂CH₂C(O)OMe, OCH₂CH₂C(O)OEt, OC(O)Me, OSO₂Me, S(O)Me, SCF₃,     S(O)CF₃OCH₂CH₂OMe, OCH₂CH₂OEt, C(O)OCH₂Ph(₂—Cl), C(O)OCH₂Ph(3-Cl),     C(O)OCH₂Ph(4-Cl) and S(O)₂CF₃; or R¹ together with R² forms a     radical —OCH₂CH₂O—, —OCF₂O— or —OCH₂OCH₂—, -   R¹ is very particularly preferably selected from the group     consisting of H, F, Cl, Br, Me, CHF₂, CF₃, OMe, OCHF₂, OCF₃ and     OCH₂CF₃.

A second embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R² is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     C₆-aryl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; or R²     together with R¹ or R³ forms a radical —OCH₂CH₂O—, —OCF₂O— or     —OCH₂OCH₂—;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R² is particularly preferably selected from the group consisting of     H, F, Cl, Br, CN, OH, NO₂, Me, iPr, CHF₂, CF₃, OMe, OEt, OPr, OiPr,     OBu, OCHF₂, OCF₃, OCH₂CF₃, C(O)OH and C(O)OMe, or R² together with     R¹ or R³ forms a radical —OCH₂CH₂O—, —OCF₂O— or —OCH₂OCH₂—; -   R² is very particularly preferably selected from the group     consisting of H, F, Cl, Me and CF₃.

A third embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R³ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     C₆-aryl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; or R³     together with R² or R⁴ forms a radical —OCH₂CH₂O—, —OCF₂O— or     —OCH₂OCH₂—;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R³ is particularly preferably selected from the group consisting of     H, halogen, OH, Me, CF₃, OMe, OCHF₂, OCF₃, OCH₂CF₃, C(O)OMe and     C(O)OEt, or R³ together with R² or R⁴ forms a radical —OCH₂CH₂O—,     —OCF₂O— or —OCH₂OCH₂—; and -   R³ is very particularly preferably selected from the group     consisting of H, F, C₁ and CF₃.

A fourth embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R⁴ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     C₆-aryl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atoms or one or two amino or (C₁-C₆)-alkylamino groups; or R⁴     together with R³ forms a radical —OCH₂CH₂O—, —OCF₂O— or —OCH₂OCH₂—;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R⁴ is particularly preferably selected from the group consisting of     H, halogen, NO₂, Me, iPr, OMe, OEt, OPr, OiPr, OBu, OCHF₂, CF₃,     OCF₃, OCH₂CF₃, OCH₂CH═CH₂ and OCH₂C≡CH, or R⁴ together with R³ forms     a radical —OCH₂CH₂O—, —OCF₂O— or —OCH₂OCH₂—; and -   R⁴ is very particularly preferably selected from the group     consisting of H, F, Cl, Me and CF₃.

A fifth embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R⁵ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     C₆-aryl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R⁵ is particularly preferably selected from the group consisting of     H, halogen, OH, NO₂, NMe₂, NEt₂, Me, Et, CHF₂, CF₃, OMe, OEt, OPr,     OiPr, OBu, OiBu, OCHF₂, OCF₃, OCH₂CF₃, C(O)OH, C(O)OMe, C(O)OEt,     C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OCH₂Ph,     OCH₂CH═CH₂, OCH₂C≡CH and C(O)OCH₂Ph(2-Cl), C(O)OCH₂Ph(3-Cl) and     C(O)OCH₂Ph(4-Cl); and -   R⁵ is very particularly preferably selected from the group     consisting of H, F, Cl, Me, CF₃, OCHF₂ and OCF₃.

In the context of the first to fifth embodiments of the present invention, it is possible to combine the specific preferred, particularly preferred and very particularly preferred meanings of the substituents R¹ to R⁵ as desired. This means that the invention comprises compounds of the formula (I) where Y is

in which, for example, the substituent R¹ has a preferred meaning and the substituents R² to R⁵ have the general meaning, or else, for example, the substituent R² has a preferred meaning, the substituent R³ has a particularly preferred meaning, the substituent R⁴ has a very particular meaning and the substituents R¹ and R⁵ have the general meaning.

A sixth embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R⁶ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, amino, (C₂-C₄)-alkenyl,     (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, hydroxy-(C₁-C₂)-alkyl,     hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl,     C_(s)-aryl, C₆-aryl-(C₁-C₂)-alkyl, C₆-aryl-(C₁-C₂)-alkoxy, phenoxy,     (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of     one another are selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁶ together form a (C₁-C₆)-alkylene group which may contain one     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another;         and -   R⁶ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, OH, NH₂, NO₂, Me, Et, Pr, iPr, tBu, CHF₂, CF₃,     Ph, OMe, OEt, OCHF₂ and OCH₂CF₃; and -   R⁶ is very particularly preferably selected from the group     consisting of F, Cl, Br, CHF₂, CF₃, OCHF₂, OCF₃ and OCH₂CF₃.

A seventh embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R⁷ is preferably selected from the group consisting of hydrogen,     (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, phenyl, phenyl-(C₁-C₂)-alkyl,     (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, where the     cycloalkyl radical is optionally substituted by (C₁-C₄)-alkyl;     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, cyano-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl,     mono-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl,     di-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl, hydroxy-(C₁-C₄)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl;     phenylsulfonyl which is optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,     (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl and (C₁-C₆)-alkylthio;     (C₁-C₄)-alkylcarbonyl; phenylcarbonyl which is optionally     substituted by one or more identical or different radicals from the     group consisting of halogen, nitro, cyano, (C₁-C₆)-alkyl,     (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy,     (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl     and (C₁-C₆)-alkylthio; pyrimidinyl-2-yl,     4,6-dimethoxypyrimidinyl-2-yl and (C₁-C₄)-alkoxycarbonyl;     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another; -   R⁷ is particularly preferably selected from the group consisting of     H, Me, Et, Pr, cPr, iPr, Bu, iBu, sBu, tBu, cPen, cHex, CHF₂,     CH₂CF₃, Ph, CH₂cPr, CH₂cPr(2-Me), CHMecPr, CH₂cBu, CH₂cPen,

CH₂cHex, CH₂Ph, CH₂CH═CH₂, CH₂C≡CH, CHMeC≡CH, CH₂C≡CMe, CH₂OMe, CH₂OEt, CH₂CH₂OH, CH₂CH₂OMe, CH₂CH₂OEt, CH₂CH₂C(O)Me, CH₂SMe, CH₂SO₂Me, CH₂CN, CH₂C(O)OMe, CH₂C(O)OEt, CH₂C(O)NH₂, CH₂C(O)NMe₂, CH₂C(O)Me, SO₂Me, SO₂Ph, C(O)Me, C(O)Ph, C(O)OMe, Ph(2-Cl), Ph(3-Cl), Ph(4-Cl), Ph(4-OMe), Ph(4-Me), Ph(4-NO₂), Ph(4-CN) and Ph(4-C(O)OMe); or R⁷ together with R⁸ forms a radical —O(CH₂)₃O—;

and

-   R⁷ is very particularly preferably selected from the group     consisting of Me, Et and CHF₂.

An eighth embodiment of the present invention comprises compounds of the formula (I) in which

Y is

and

-   R⁸ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy,     hydroxy-(C₁-C₂)-alkyl, hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy,     cyano-(C₁-C₂)-alkyl, C₆-aryl, C₆-aryl-(C₁-C₂)-alkyl,     C₆-aryl-(C₁-C₂)-alkoxy, phenoxy, (C₁-C₄)-alkylcarbonyloxy,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of     one another are selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups; or R⁸ together with R⁷ forms a radical —O(CH₂)₃O—,     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another and -   R⁸ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, OH, NH₂, NO₂, Me, Et, CHF₂, CF₃, OCHF₂,     OCH₂CF₃, OMe, OEt, OPr, OiPr, OBu, OtBu, SO₂Me, SO₂iPr,     3-oxetanyloxy, OPh, OPh(2-Cl), OPh(3-Cl), OPh(4-Cl), OPh(3-OMe),     OPh(4-Me), OPh(4-OMe), OCH₂CHF₂, OCH₂CN, OCH₂Ph, SEt, SO₂Et, SO₂Ph,     NMe₂, OcHex, OCH₂Pr, OCH₂Pen, OCH₂cHex, OcPen, OC(O)Me, CH₂cPen,     CH₂cHex, CH₂CH═CH₂, CH₂C≡CH, CHMeC≡CH, CH₂C≡CMe, CH₂OMe, CH₂OEt,     CH₂CH₂OH, CH₂CH₂OMe, CH₂CH₂OEt, CH₂SMe, CH₂SO₂Me, OCH₂CH═CH₂ and     OCH₂C≡CH; and -   R⁸ is very particularly preferably selected from the group     consisting of F, Cl, CHF₂, CF₃, OCHF₂ and OCH₂CF₃.

In the context of the sixth to eighth embodiments of the present invention, it is possible to combine the specific preferred, particularly preferred and very particularly preferred meanings of the substituents R⁶ to R⁸. This means that the invention comprises compounds of the formula (I) where Y is

in which, for example, the substituent R⁶ has a preferred meaning and the substituents R⁷ and R⁸ have the general meaning, or else the substituent R⁷ has a preferred meaning, the substituent R⁸ has a particularly preferred meaning and the substituent R⁶ has a very particular meaning.

In the context of the present invention, the compounds of the formula (I) also comprise compounds quaternized at a nitrogen atom by a) protonation, b) alkylation or c) oxidation.

If appropriate, the compounds of the formula (I) may also be able to form salts by forming an adduct with a suitable inorganic or organic acid, such as, for example, HCl, HBr, H₂SO₄ or HNO₃, or else oxalic acid or sulfonic acids, to a basic group, such as, for example, amino or alkylamino. Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, are capable of forming inner salts with groups, such as amino groups, which can be protonated for their part. Salts can also be formed by replacing the hydrogen of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, with a cation suitable in the agrochemical sector. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, especially sodium salts and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts having cations of the formula [NRR′R″R′″]⁺ in which R to R′″ in each case independently are an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.

In the formula (I) and in all the other formulae of the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless indicated specifically, preference is given for these radicals to the lower carbon skeletons, for example those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms. Alkyl radicals, also in composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl; propyls, such as n-propyl or isopropyl; butyls, such as n-, iso-, t- or 2-butyl; pentyls, such as n-pentyl, isopentyl or neopentyl; hexyls, such as n-hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl; heptyls, such as n-heptyl, 1-methylhexyl or 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; where at least one double bond or triple bond is present, preferably one double bond or triple bond, respectively. Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.

Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkyl groups can be present in bi- or tricyclic form.

If haloalkyl groups and haloalkyl radicals of haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl etc. are stated, the lower carbon skeletons of these radicals having, for example, 1 to 6 carbon atoms or 2 to 6 carbon atoms, in particular 1 to 4 carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals are in each case straight-chain or branched in the carbon skeleton. Examples are difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl.

Alkylene groups in these radicals are the lower carbon skeletons, for example those having 1 to 10 carbon atoms, in particular 1 to 6 carbon atoms, or preferably 2 to 4 carbon atoms, and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples are methylene, ethylene, n- and isopropylene and n-, s-, iso-, t-butylene.

Hydroxyalkyl groups in these radicals are the lower carbon skeletons, for example those having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples of these are 1,2-dihydroxyethyl and 3-hydroxypropyl.

Halogen is fluorine, chlorine, bromine or iodine; haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl and alkynyl, respectively, which are fully or partially substituted by halogen, preferably by fluorine, chlorine or bromine, in particular by fluorine and/or chlorine, examples being monohaloalkyl, perhaloalkyl, CF₃, CHF₂, CH₂F, CF₃CF₂, CH₂FCHCl, CCl₃, CHCl₂, CH₂CH₂Cl; haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, CF₃CF₂O, OCH₂CF₃, and OCH₂CH₂Cl; this correspondingly applies to haloalkenyl and other halogen-substituted radicals.

Aryl is a monocyclic, bicyclic or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl.

The definition “substituted by one or more radicals” refers, unless otherwise defined, to one or more identical or different radicals.

The substituents given by way of example (“first substituent level”) can, if they include hydrocarbon-containing fractions, be further substituted therein if desired (“second substituent level”), by for example one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. The term “substituted radical” preferably embraces just one or two substituent levels.

In the case of radicals having carbon atoms, preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C₁-C₄)-alkyl, preferably methyl or ethyl, (C₁-C₄)-haloalkyl, preferably trifluoromethyl, (C₁-C₄)-alkoxy, preferably methoxy or ethoxy, (C₁-C₄)-haloalkoxy, nitro and cyano.

Optionally substituted aryl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical of different radicals from the group consisting of halogen, (C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Primarily for reasons of higher herbicidal activity, better selectivity and/or better producibility, compounds of the formula (I) according to the invention or their agrochemical salts or quaternary N derivatives are of particular interest in which individual radicals have one of the preferred meanings already specified or specified below, or in particular those in which one or more of the preferred meanings already specified or specified below occur in combination.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or the intermediates required in each case for the preparation. These radical definitions can be exchanged for one another as desired, i.e. including combinations between the given preferred ranges.

The present compounds of the formula (I) have a chiral sulfur atom which, in the structure shown above, is illustrated by the marker (*). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have either an (R) configuration or an (S) configuration.

The present invention encompasses compounds of the formula (I) both with (S) and with (R) configuration, i.e. the present invention encompasses the compounds of the formula (I) in which the sulfur atom in question has

-   (1) an (R) configuration; or -   (2) an (S) configuration.

In addition, the scope of the present invention also encompasses

-   (3) any mixtures of compounds of the formula (I) having an (R)     configuration (compounds of the formula (I-(R)) with compounds of     the formula (I) having an (S) configuration (compounds of the     formula (I-(S)),     where a racemic mixture of the compounds of the formula (I)     having (R) and (S) configuration is excluded from the present     invention.

However, within the context of the present invention, preference is given to using in particular compounds of the formula (I) having (S) configuration (compounds of the formula (I-S)) as compared to the (R) configuration (compounds of the formula (I-R)) with a selectivity of 60 to 100%, preferably 80 to 100%, in particular 90 to 100%, very particularly preferably 95 to 100%, where the particular (S) compound is preferably present with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) compound in question.

Accordingly, the present invention relates in particular to compounds of the formula (I) in which the stereochemical configuration on the sulfur atom(s) marked by (*) is present with a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S), in particular 90 to 100% (S), very particularly 95 to 100% (S).

Depending on the type and attachment of the substituents, the compounds of the formula (I) may contain further centers of chirality in addition to the sulfur atom marked (*) in formula (I), in which case they are then present as stereoisomers. In the context of the present invention, the definition of the formula (I) comprises all stereoisomers, such as enantiomers, diasteromers and Z and E isomers, defined by their specific spatial form, i.e. the present invention comprises both the pure stereoisomers and less pure mixtures thereof. Here, preference is given in particular to compounds which, at the sulfur atom marked (*), have a stereochemical purity of from 60 to 100% (S), preferably from 80 to 100% (S), in particular from 90 to 100% (S), very particularly from 95 to 100% (S), and, at the remaining further stereocenters, are present in racemic form or in a more or less pronounced stereochemical purity.

If, for example, one or more alkenyl groups are present, there may be diastereomers (Z and E isomers).

If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers.

Corresponding stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. Accordingly, the invention also relates to all stereoisomers embraced by the formula (I) but not shown in their specific stereoform, and to their mixtures.

For the possible combinations of the various substituents of the formula (I) the general principles of the construction of chemical compounds have to be observed, i.e. the formula (I) does not comprise any compounds known to the person skilled in the art as being chemically impossible.

The present invention furthermore provides processes for preparing corresponding compounds of the formula (I) and/or salts thereof and/or agrochemically acceptable quaternized nitrogen derivatives thereof:

-   a.) To prepare optically active sulfoxides of the formula (I), for     example, a thioether of the formula (II)

-   -   in which Y has the meaning given above for formula (I) is         oxidized with one equivalent of an oxidizing agent to the         sulfoxide of the formula (I).

-   -   The oxidizing agents which can be used for this reaction are not         subject to any particular limitations, and it is possible to use         any oxidizing agent capable of oxidizing the sulfur compounds in         question to sulfoxide compounds. Oxidizing agents suitable for         preparing the sulfoxides are inorganic peroxides, such as, for         example, hydrogen peroxide, sodium metaperiodate, organic         peroxides, such as, for example, tert-butyl hydroperoxide, or         organic peracids, such as peracetic acid or, preferably,         3-chloroperbenzoic acid. The reaction can be carried out in         halogenated hydrocarbons, for example dichloromethane,         1,2-dichloroethane, an alcohol, such as, for example, methanol,         or in dimethylformamide, water or acetic acid, or in a mixture         of the solvents mentioned above. The reaction can be carried out         in a temperature range of between −80° C. and 120° C.,         preferably between −20° C. and 50° C. Such processes are known         in the literature and described, for example, in J. Org. Chem.,         58 (1993) 2791, J. Org. Chem., 68 (2003) 3849 and J.         Heterocyclic Chem., 15 (1978) 1361, any relevant disclosure is         incorporated by reference into the present invention.     -   The preparation of the thioether of the formula (II) is known,         for example, from WO 01/12613 A, WO 02/62770 A, WO 03/00686 A         and WO 03/10165 A.

-   b) Compounds of the formula (I) can additionally be prepared by     processes as described, for example, in WO 2001/012613, WO     2002/062770, WO 2003/000686, WO 2004/013106, WO 2006/024820, WO     2007/003294 and WO 2007/003295.

-   c) The enantioselective synthesis of chiral sulfoxides of the     formula (I) in optically enriched or pure form can be carried out     from thio compounds of the formula (II) using methods as described,     for example, in Chem. Rev., 103 (2003) 3651-3705 and in the     literature cited therein. The corresponding disclosure of this     literature reference is incorporated into the present invention by     way of reference. Here, in each individual case, the absolute     configuration of the product depends on the structure of the     optically active catalyst.

Corresponding salts can be prepared in a manner known per se to the person skilled in the art.

Compounds of the formula (Ia)

consist of a mixture of the respective enantiomers (Ia-S) and (Ia-R) which are chiral at the sulfoxide function

where the radicals R¹, R², R³, R⁴ and R⁵ have the meanings given above for the formula (I).

Compounds of the formula (Ib)

consist of a mixture of the respective enantiomers (Ib-S) and (Ib-R) which are chiral at the sulfoxide function

where the radicals R⁶, R⁷ and R⁸ have the meanings given above for the formula (I).

Suitable for preparing enantiomers of the formula (I) are, in addition to enantioselective syntheses, also customary methods for the separation of racemates (cf. textbooks of stereochemistry).

Racemic mixtures, for example of optically active sulfoxides of the formula (I), can be separated by known processes. Such methods for the separation of racemates are described in textbooks of stereochemistry, for example in “Basic Organic Stereochemistry” (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001; John Wiley & Sons) and “Stereochemisty of Organic Compounds (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N.; 1994; John Wiley & Sons), the relevant disclosure of which is incorporated by reference into the present invention. Suitable for this purpose are, for example, adduct formation with an optically active auxiliary, separation of the diastereomeric adducts into the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, if appropriate under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers to afford the enantiomers. Suitable for preparative amounts or on an industrial scale are processes such as the crystallization of diastereomeric salts which can be obtained from the compounds (I) using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases.

Optically active acids which are suitable for racemate separation by crystallization of diastereomeric salts are, for example, camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids; suitable optically active bases are, for example, quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases.

The crystallizations are then in most cases carried out in aqueous or aqueous-organic solvents, where the diastereomer which is less soluble precipitates first, if appropriate after seeding. One enantiomer of the compound of the formula (I) is then liberated from the precipitated salt, or the other is liberated from the crystals, by acidification or using a base.

Furthermore, racemates can be separated chromatographically using chiral stationary phases. Such enantiomer separations can be carried out in the mg to 100 kg range using preparative HPLC units operated batch-wise or continuously.

The “inert solvents” referred to in the above process variants are in each case solvents which are inert under the particular reaction conditions, i.e. do not react with the starting materials in particular, but need not be inert under all reaction conditions.

Libraries of compounds of the formula (I) and/or salts thereof which can be synthesized by the aforementioned reactions can also be prepared in a parallel manner, it being possible for this to take place in a manual, partly automated or completely automated manner. In this connection, it is, for example, possible to automate the reaction procedure, the work-up or the purification of the products and/or intermediates. Overall, this is understood as meaning a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Gunther Jung), Verlag Wiley 1999, on pages 1 to 34.

For the parallel reaction procedure and work-up, it is possible to use a series of commercially available instruments, for example Calpyso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MuItiPROBE Automated Workstations from Perkin Elmer, Waltham, Mass. 02451, USA. For the parallel purification of compounds of the formula (I) and salts thereof or of intermediates produced during the preparation, there are available, inter alia, chromatography apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses listed lead to a modular procedure in which the individual process steps are automated, but between the process steps manual operations have to be carried out. This can be circumvented by using partly or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be acquired, for example, from Caliper, Hopkinton, Mass. 01748, USA.

The implementation of single or several synthesis steps can be supported through the use of polymer-supported reagents/scavenger resins. The specialist literature describes a series of experimental protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

Besides the methods described here, the preparation of compounds of the formula (I) and salts thereof can take place completely or partially by solid-phase supported methods. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bonded to a synthesis resin. Solid-phase supported synthesis methods are sufficiently described in the specialist literature, e.g. Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998 and Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Gunther Jung), Verlag Wiley, 1999. The use of solid-phase supported synthesis methods permits a series of protocols known in the literature, which again can be carried out manually or in an automated manner. For example, the “teabag method” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl. Acad. Sci., 1985, 82, 5131-5135), in which products from IRORI, 11149 North Torrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may be semiautomated. The automation of solid-phase-supported parallel syntheses is performed successfully, for example, by apparatuses from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif. 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany. The reactions can be carried out, for example, by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, Calif. 92064, USA.

Both on a solid phase and in liquid phase can the procedure of individual or several synthesis steps be supported through the use of microwave technology. The specialist literature describes a series of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Verlag Wiley, 2005.

The preparation according to the process described here produces compounds of the formula (I) and their salts in the form of substance collections which are called libraries. The present invention also provides libraries which comprise at least two compounds of the formula (I) and their salts.

On account of the herbicidal property of the compounds of the formula (I), the invention also further provides the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants.

The compounds of the formula (I) according to the invention and their salts, also referred to synonymously below together as compounds of the formula (I), have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Difficult-to-control perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs are also well controlled by the active compounds. Here, it is immaterial whether the substances are applied by the presowing method, the pre-emergence method or the post-emergence method.

Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds of the formula (I) according to the invention, without the enumeration being restricted to certain species.

On the side of the monocotyledonous weed species, e.g. Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, Ischaemum, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria, Sphenoclea, and also Cyperus species predominantly from the annual group and on the sides of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species are well controlled.

In the case of dicotyledonous weed species, the spectrum of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds. Moreover, herbicidal effect in the case of dicotyledonous weeds such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Emex, Galeopsis, Galinsoga, Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa, Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium is observed.

If the compounds of the formula (I) according to the invention are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.

If the active compounds of the formula (I) are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment, and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

Although the compounds of the formula (I) according to the invention have excellent herbicidal activity in respect of monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, corn, sugarbeet, cotton, oilseed rape and soybean, are only damaged negligibly, if at all. This is why the present compounds are highly suitable for the selective control of unwanted plant growth in agriculturally useful plants.

In addition, the substances of the formula (I) according to the invention have excellent growth regulatory properties in crop plants. They engage in the plant metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since lodging can be reduced, or prevented completely, hereby.

By virtue of their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of known genetically modified plants or genetically modified plants still to be developed. In general, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storeability, composition and specific constituents. Thus, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition. Other particular properties may be tolerance or resistance to abiotic stressors, for example heat, low temperatures, drought, salinity and ultraviolet radication.

It is preferred to use the compounds of the formula (I) according to the invention or salts thereof in economically important transgenic crops of useful plants and ornamental plants, for example of cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassaya and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.

It is preferred to be able to employ the compounds of the formula (I) as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.

Conventional methods of generating novel plants which have modified properties in comparison to plants occurring to date consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, the following have been described in several cases:

-   -   recombinant modifications of crop plants for the purposes of         modifying the starch synthesized in the plants (for example WO         92/011376, WO 92/014827, WO 91/019806),     -   transgenic crop plants which are resistant to certain herbicides         of the glufosinate type (cf., for example, EP 0242236,         EP 0242246) or the glyphosate type (WO 92/000377) or the         sulfonylurea type (EP 0257993, U.S. Pat. No. 5,013,659),     -   transgenic crop plants, for example cotton, which is capable of         producing Bacillus thuringiensis toxins (Bt toxins), which make         the plants resistant to certain pests (EP 0142924, EP 0193259),     -   transgenic crop plants with a modified fatty acid composition         (WO 91/013972).     -   genetically modified crop plants with novel constituents or         secondary metabolites, for example novel phytoalexins, which         bring about an increased disease resistance (EP 0309862, EP         0464461),     -   genetically modified plants with reduced photorespiration which         feature higher yields and higher stress tolerance (EP 0305398),     -   transgenic crop plants which produce pharmaceutically or         diagnostically important proteins (“molecular pharming”),     -   transgenic crop plants which are distinguished by higher yields         or better quality,     -   transgenic crop plants which are distinguished by a combination,         for example of the abovementioned novel properties (“gene         stacking”).

A large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generated are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. oder Christou, “Trends in Plant Science” 1 (1996) 423-431).

To carry out such recombinant manipulations, nucleic acid molecules which allow mutagenesis or sequence changes by recombination of DNA sequences can be introduced into plasmids. For example, base substitutions can be carried out, part-sequences can be removed, or natural or synthetic sequences may be added with the aid of standard methods. To link the DNA fragments with one another, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene and Klone”, VCH Weinheim 2nd ed., 1996.

For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.

To this end, it is possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and also DNA molecules which only encompass portions of the coding sequence, it being necessary for these portions to be long enough to have an antisense effect in the cells. The use of DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them, is also possible.

When expressing nucleic acid molecules in plants, the protein synthesized can be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to link the coding region with DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules can also be expressed in the organelles of the plant cells.

The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants can be plants of any desired plant species, i.e. not only monocotyledonous, but also dicotyledonous, plants.

Thus, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or the expression of heterologous (=foreign) genes or gene sequences.

It is preferred to employ the compounds of the formula (I) according to the invention in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or against herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or against herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active substances.

When the active compounds of the formula (I) according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.

The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds of the formula (I) can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Kuchler, “Chemische Technologie” [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation assistants, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Åthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to produce combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a tank mix.

Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltauride. To prepare the wettable powders, the herbicidally active compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills and simultaneously or subsequently mixed with the formulation assistants.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: alkylarylsulfonic calcium salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, as have for example already been listed above in connection with the other types of formulation.

Granules can be prepared either by spraying the active compound onto granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.

Water-dispersible granules are prepared generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the preparation of pan, fluidized bed, extruder and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, p. 8-57.

For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations comprise generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).

In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation components. In the case of emulsifiable concentrates, the active compound concentration can be from about 1 to 90, preferably from 5 to 80, % by weight. Dust-type formulations contain from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In the case of water-dispersible granules, the active compound content depends partially on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active compound formulations mentioned optionally comprise the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.

The compounds of the formula (I) or salts thereof can be employed as such or in the form of their preparations (formulations) combined with other pesticidally active compounds, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example as finished formulation or as tank mixes. Combination partners which can be used for the active compounds of the formula (I) according to the invention in mixture formulations or in the tank mix are, for example, known active compounds whose action is based on the inhibition of, for example,

acetolactate synthase, acetyl-coenzyme-A carboxylase, PS I, PS II, HPPDO, phytoene desaturase, protoporphyrinogen oxidase, glutamine synthetase, 5-enolpyruvylshikimate 3-phosphate synthetase or cellulose biosynthesis. Such compounds and also other compounds that can be used, some of which having an unknown or other mechanism of action, are described, for example, in Weed Research 26, 441-445 (1986), or “The Pesticide Manual”, 11th edition 1997 (hereinbelow also referred to abbreviated as “PM”) and 12th edition 2000, The British Crop Protection Council and the Royal Soc. of Chemistry (publisher), and the literature cited therein. Herbicides known from the literature which can be combined with the compounds of the formula (I) are, for example, the following active compounds (note: the compounds are referred to either by the “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number):

acetochlor; acifluorfen(-sodium); aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetic acid and methyl [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate, acrolein; alachlor; alloxydim(-sodium); ametryn; amicarbazone, amidochlor, amidosulfuron; aminopyralid, amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam; atraton; atrazine; azafenidin, azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BCPC; beflubutamid, benazolin(-ethyl); benfluralin; benfuresate; bensulfuron(-methyl); bensulide; bentazone; benzfendizone; benzobicyclon, benzofenap; benzofluor; benzoylprop(-ethyl); benzthiazuron; bifenox; bialaphos; bifenox; bispyribac(-sodium), borax; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butafenacil, butamifos; butenachlor; buthidazole; butralin; butroxydim, butylate; cacodylic acid; calcium chlorate; cafenstrole (CH-900); carbetamide; carfentrazone(-ethyl); caloxydim, CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chlorallyl diethyldithiocarbamate; chlorflurenol (-methyl); chlomethoxyfen; clethodim; clomeprop; chloramben; chlorazifop-butyl, chlormesulon; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron(-ethyl); chloroacetic acid; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal(-dimethyl); chlorthiamid; chlortoluron, cinidon(-methyl and -ethyl), cinmethylin; cinosulfuron; cisanilide; clefoxydim, clethodim; clodinafop and its ester derivatives (for example clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; clopyrasulfuron(-methyl); cloransulam(-methyl), cresol; cumyluron (JC 940); cyanamide; cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (for example the butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-D, 2,4-DB, 3,4-DA, 3,4-DB, 2,4-DEB, dalapon; dazomed; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; ortho-dichlorobenzene; para-dichlorobenzene; dichlorprop; dichlorprop-P; diclofop and its esters, such as diclofop-methyl; diclosulam, diethatyl(-ethyl); difenoxuron; difenzoquat; difenzoquat-methylsulfate; diflufenican; diflufenzopyr, dimefuron; dimepiperate, dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethenamid-P; dimethazone, dimexyflam, dimethipin; dimethylarsinic acid; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; diquat-dibromide; dithiopyr; diuron; DNOC; 3,4-DP; DSMA; EBEP; eglinazine-ethyl; EL77, i.e. 5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide; endothal; epoprodan, EPTC; esprocarb; ethalfluralin; ethametsulfuron(-methyl); ethidimuron; ethiozin; ethofumesate; ethoxyfen and its esters (for example the ethyl ester, HN-252); ethoxysulfuron, etobenzanid (HW 52); F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide; fenoprop; fenoxan, fenoxapropand fenoxaprop-P and also their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fentrazamide, fenuron; ferrous sulfate; flamprop(-methyl or -isopropyl or -isopropyl-L); flazasulfuron; floazulate, florasulam, fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluazolate; flucarbazone(-sodium), flucetosulfuron; fluchloralin; flufenacet; flufenpyr(-ethyl); flumetsulam; flumeturon; flumiclorac(-pentyl), flumioxazin (S-482); flumipropyn; fluometuron, fluorochloridone, fluorodifen; fluoroglycofen(-ethyl); flupoxam (KNW-739); flupropacil (UBIC-4243); flupropanate, flupyrsulfuron(-methyl or -sodium), flurenol(-butyl), fluridone; fluorochloridone; fluoroxypyr(-meptyl); flurprimidol; flurtamone; fluthiacet(-methyl) (KIH-9201); fluthiamide; fomesafen; foramsulfuron; fosamine; furyloxyfen; glufosinate(-ammonium); glyphosate(-isopropylammonium); halosafen; halosulfuron(-methyl) and its esters (for example the methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (=R-haloxyfop) and its esters; HC-252; hexazinone; imazamethabenz(-methyl); imazapyr; imazaquin and salts, such as the ammonium salt; imazamethapyr, imazamox, imazapic, imazethamethapyr; imazethapyr; imazosulfuron; indanofan, iodomethane; iodosulfuron(methylsodium); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxachlortole, isoxaflutole, isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MAA; MAMA; MCPA; MCPA-2-ethylhexyl; MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; mefenacet; mefluidid; mesosulfuron(-methyl); mesotrione, metamifop; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methylarsonic acid; methyldymron; methyl isothiocyanate; metabenzuron, metamifop; methobenzuron; metobromuron; (alpha-)metolachlor; S-metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MK-616; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MSMA; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; nonanoic acid; norflurazon; oleic acid (fatty acid); orbencarb; orthosulfamuron; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron, oxaziclomefone, oxyfluorfen; paraquat; paraquat-dichloride; pebulate; pelargonic acid, pendimethalin; penoxsulam; pentachlorophenol; pentanochlor; pentoxazone, perfluidone; phenisopham; phenmedipham(ethyl); pethoxamid; picloram; picolinafen, pinoxaden, piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron(-methyl); potassium arsenite; potassium azide; procarbazone-(sodium), procyazine; prodiamine; profluazol; profluralin; profoxydim; proglinazine(-ethyl); prometon; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propoxycarbazone(-sodium) (BAY MKH 6561); propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraclonil; pyraflufen(-ethyl), pyrasulfotole; pyrazolinate; pyrazon; pyrazosulfuron(-ethyl); pyrazoxyfen; pyribambenz-isopropyl; pyribenzoxim, pyributicarb, pyridafol, pyridate; pyriftalid; pyrimidobac(-methyl), pyrimisulfan, pyrithiobac(-sodium) (KIH-2031); pyroxasulfone; pyroxofop and its esters (for example the propargyl ester); pyroxsulam (triflosulam); quinclorac; quinmerac; quinoclamine, quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and methyl 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoate; SMA; sodium arsenite; sodium azide; sodium chlorate; sulcotrione, sulfentrazon (FMC-97285, F-6285); sulfazuron; sulfometuron(-methyl); sulfosate (ICI-A0224); sulfosulfuron, 2,3,6-TBA; TCA(sodium); tebutam (GCP-5544); tebuthiuron; tefuryltrione, tembotrione, tepraloxydim, terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiafluamide, thiazafluoron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiencarbazone-methyl, thifensulfuron(-methyl); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron(-methyl); tricamba; triclopyr; tridiphane; trietazine; trifloxysulfuron(sodium); trifluralin; triflusulfuron and esters (for example the methyl ester, DPX-66037); trihydroxytriazine; trimeturon; tritosulfuron; tropamezone; tsitodef; vernolate; [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole, UBH-509; D-489; LS 82-556, i.e. [(S)-3-N-(methylbenzyl)carbamoyl-5-propionyl-2,6-lutidine]; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; ET-751, i.e. h ethyl [2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorophenoxy]acetate; KIH-6127, i.e. pyriminobac-methyl; KIH-2023, i.e. bispyribac-sodium; and SYP-249, i.e ethyl 2-{2-nitro-5-[(2-chloro-4-trifluoromethyl)phenoxy]benzoxy}-3-methyl-3-butenoate, SYN-523.

Of particular interest is the selective control of harmful plants in crops of useful plants and ornamentals. Although the compounds of the formula (I) according to the invention have already demonstrated very good to adequate selectivity in a large number of crops, in principle, in some crops and in particular also in the case of mixtures with other, less selective herbicides, phytotoxicities on the crop plants may occur. In this connection, combinations of compounds of the formula (I) according to the invention are of particular interest which comprise the compounds of the formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, millet), sugar beet, sugar cane, oilseed rape, cotton and soybeans, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I) alone or else in their combinations with further pesticides:

-   a) compounds of the formulae (S-II) to (S-IV) -   where the symbols and indices have the following meanings:

-   n′ is a natural number from 0 to 5, preferably from 0 to 3; -   T is a (C₁— or C₂)-alkanediyl chain which is unsubstituted or     substituted by one or two (C₁-C₄)-alkyl radicals or by     [(C₁-C₃)-alkoxy]carbonyl; -   W is an unsubstituted or substituted divalent heterocyclic radical     from the group consisting of partially unsaturated or aromatic     five-membered heterocycles having 1 to 3 hetero ring atoms of the     type N or O, where at least one nitrogen atom and at most one oxygen     atom is present in the ring, preferably a radical from the group     consisting of (W1) to (W4),

-   m′ is 0 or 1; -   R¹⁷, R¹⁹ are identical or different and are halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, nitro or (C₁-C₄)-haloalkyl; -   R¹⁸, R²⁰ are identical or different and are OR²⁴, SR²⁴ or NR²⁴R²⁵ or     a saturated or unsaturated 3- to 7-membered heterocycle having at     least one nitrogen atom and up to 3 heteroatoms, preferably from the     group consisting of O and S, which is attached via the nitrogen atom     to the carbonyl group in (S-II) or (S-III) and is unsubstituted or     substituted by radicals from the group consisting of (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy or optionally substituted phenyl, preferably a     radical of the formula OR²⁴, NHR²⁵ or N(CH₃)₂, in particular of the     formula OR²⁴; -   R²⁴ is hydrogen or an unsubstituted or substituted aliphatic     hydrocarbon radical having preferably a total of 1 to 18 carbon     atoms; -   R²⁵ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or substituted or     unsubstituted phenyl; -   R^(X′) is H, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₈)-alkyl, cyano or COOR²⁶ where R²⁶ is hydrogen,     (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₁₂)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl; -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₃-C₁₂)-cycloalkyl or substituted     or unsubstituted phenyl; -   R²¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,     (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably dichloromethyl; -   R²², R²³ are identical or different and are hydrogen, (C₁-C₄)-alkyl,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,     (C₂-C₄)-haloalkenyl, (C₁-C₄)-alkylcarbamoyl-(C₁-C₄)-alkyl,     (C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, dioxolanyl-(C₁-C₄)-alkyl, thiazolyl,     furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted     phenyl, or R²² and R²³ together form a substituted or unsubstituted     heterocyclic ring, preferably an oxazolidine, thiazolidine,     piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; -   b) one or more compounds from the group consisting of:     -   1,8-naphthalic anhydride,     -   methyl diphenylmethoxyacetate,     -   1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron),     -   O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton),     -   4-chlorophenyl methylcarbamate (mephenate),     -   O,O-diethyl O-phenyl phosphorothioate (dietholate),     -   4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415,         CAS-Regno: 31541-57-8),     -   cyanomethoxyimino(phenyl)acetonitrile (cyometrinil)     -   1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),     -   4′-chloro-2,2,2-trifluoroacetophenone         O-1,3-dioxolan-2-ylmethyloxime (fluxofenim),     -   4,6-dichloro-2-phenylpyrimidine (fenclorim),     -   benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate         (flurazole),     -   2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),     -   N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),     -   (2,4-dichlorophenoxy)acetic acid (2,4-D),     -   (4-chlorophenoxy)acetic acid,     -   (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),     -   4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),     -   (4-chloro-o-tolyloxy)acetic acid (MCPA),     -   4-(4-chloro-o-tolyloxy)butyric acid,     -   4-(4-chlorophenoxy)butyric acid,     -   3,6-dichloro-2-methoxybenzoic acid (dicamba),     -   1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate         (lactidichlor) and their salts and esters, preferably (C₁-C₈); -   c) N-acylsulfonamides of the formula (S-V) and their salts,

in which

-   R³⁰ is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a     hydrocarbonthio radical or a heterocyclyl radical which is     preferably attached via a carbon atom, where each of the 4     last-mentioned radicals is unsubstituted or substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl,     carbonamide, sulfonamide and radicals of the formula —Z^(a′)—R^(a′),     -   where each hydrocarbon moiety has preferably 1 to 20 carbon         atoms and a carbon-containing radical R³⁰ including substituents         has preferably 1 to 30 carbon atoms; -   R³¹ is hydrogen or (C₁-C₄)-alkyl, preferably hydrogen, or -   R³⁰ and R³¹ together with the group of the formula —CO—N— are the     radicals of a 3- to 8-membered saturated or unsaturated ring; -   R³² are identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH₂,     SO₂NH₂ or a radical of the formula —Z^(b′)—R^(b′); -   R³³ is hydrogen or (C₁-C₄)-alkyl, preferably H; -   R³⁴ are identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂     and a radical of the formula —Z^(c′)—R^(c′); -   R^(a′) is a hydrocarbon radical or a heterocyclyl radical, where     each of the two last-mentioned radicals is unsubstituted or     substituted by one or more identical or different radicals from the     group consisting of halogen, cyano, nitro, amino, hydroxyl, mono-     and di-[(C₁-C₄)-alkyl]amino, or an alkyl radical in which a     plurality, preferably 2 or 3, non-adjacent CH₂ groups are in each     case replaced by an oxygen atom; -   R^(b′),R^(c′) are identical or different and are a hydrocarbon     radical or a heterocyclyl radical, where each of the two     last-mentioned radicals is unsubstituted or substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, phosphoryl,     halo-(C₁-C₄)-alkoxy, mono- and di-[(C₁-C₄)-alkyl]amino, or an alkyl     radical in which a plurality, preferably 2 or 3, non-adjacent CH₂     groups are in each case replaced by an oxygen atom;     -   Z^(a′) is a divalent group of the formula —O—, —S—, —CO—, —CS—,         —CO—O—, —CO—S—, —O—CO—, —S—CO—, —SO—, —SO₂—, —NR*-, —CO—NR*-,         —NR*—CO—, —SO₂—NR*- or —NR*—SO₂—, where the bond indicated on         the right-hand side of the divalent group in question is the         bond to the radical R^(a) and where the R* in the 5         last-mentioned radicals independently of one another are each H,         (C₁-C₄)-alkyl or halo-(C₁-C₄)-alkyl; -   Z^(b′),Z^(c′) independently of one another are a direct bond or a     divalent group of the formula —O—, —S—, —CO—, —CS—, —CO—O—, —CO—S—,     —O—CO—, —S—CO—, —SO—, —SO₂—, —NR*-, —SO₂—NR*-, —NR*—SO₂—, —CO—NR*-     or —NR*—CO—, where the bond indicated on the right-hand side of the     divalent group in question is the bond to the radical R^(b′) or     R^(c′) and where R* in the 5 last-mentioned radicals independently     of one another are each H, (C₁-C₄)-alkyl or halo-(C₁-C₄)-alkyl; -   n is an integer from 0 to 4, preferably 0, 1 or 2, particularly     preferably 0 or 1, and -   m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular     0, 1 or 2; -   d) acylsulfamoylbenzamides of the formula (S-VI), if appropriate     also in salt form,

in which

-   X³ is CH or N, -   R³⁵ is hydrogen, heterocyclyl or a hydrocarbon radical where the two     last-mentioned radicals are optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂     and Z^(a′)—R^(a′); -   R³⁶ is hydrogen, hydroxyl, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl,     (C₂-C₆)-alkynyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy, where the five     last-mentioned radicals are optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and     (C₁-C₄)-alkylthio, or -   R³⁵ and R³⁶ together with the nitrogen atom that carries them are a     3- to 8-membered saturated or unsaturated ring; -   R³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂,     SO₂NH₂ or Z^(b′)—R^(b′); -   R³⁸ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or (C₂-C₄)-alkynyl; -   R³⁹ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl,     CHO, CONH₂, SO₂NH₂ or Z^(c)—R^(c); -   R^(a′) is a (C₂-C₂₀)-alkyl radical whose carbon chain is interrupted     once or more than once by oxygen atoms, is heterocyclyl or a     hydrocarbon radical, where the two last-mentioned radicals are     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, cyano, nitro, amino,     hydroxyl, mono- and di-[(C₁-C₄)-alkyl]amino; -   R^(b′),R^(c′) are identical or different and are a (C₂-C₂₀)-alkyl     radical whose carbon chain is interrupted once or more than once by     oxygen atoms, are heterocyclyl or a hydrocarbon radical, where the     two last-mentioned radicals are optionally substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, phosphoryl,     (C₁-C₄)-haloalkoxy, mono- and di-[(C₁-C₄)-alkyl]amino; -   Z^(a′) is a divalent unit from the group consisting of O, S, CO, CS,     C(O)O, C(O)S, SO, SO₂, NR^(d′), C(O)NR^(d′) and SO₂NR^(d′); -   Z^(b′),Z^(c′) are identical or different and are a direct bond or     divalent unit from the group consisting of O, S, CO, CS, C(O)O,     C(O)S, SO, SO₂, NR^(d′), SO₂NR^(d′) and C(O)NR^(d′); -   R^(d′) is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl; -   N is an integer from 0 to 4, and -   m if X═CH is an integer from 0 to 5, and if X═N is an integer from 0     to 4; -   e) compounds of the type of the acylsulfamoylbenzamides, for example     of the formula (S-VII) below, which are known, for example, from WO     99/16744,

-   for example those in which     -   R²¹=cyclopropyl and         R²²=H(S-3-1=4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide),     -   R²¹=cyclopropyl and R²²=5-Cl (S-3-2),     -   R²¹=ethyl and R²²=H(S-3-3),     -   R²¹=isopropyl and R²²=5-Cl (S-3-4) and     -   R²¹=isopropyl and R²²=H(S-3-5); -   f) compounds of the type of the N-acylsulfamoylphenylureas of the     formula (S-VIII), which are known, for example, from EP-A-365484

in which

-   A is a radical from the group consisting of

-   R^(α′) and R^(β′) independently of one another are hydrogen or     (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl,

or (C₁-C₄)-alkoxy or

substituted by C₁-C₄)-alkoxy or

-   R^(α′) and R^(β′) together are a (C₄-C₆)-alkylene bridge or a     (C₄-C₆)-alkylene bridge which is interrupted by oxygen, sulfur, SO,     SO₂, NH or —N((C₁-C₄)-alkyl)-, -   R^(γ′) is hydrogen or (C₁-C₄)-alkyl, -   R^(a′) and R^(b′) independently of one another are hydrogen,     halogen, cyano, nitro, trifluoromethyl, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, —COOR^(j), —CONR^(k′)R^(m′), —COR^(n′),     —SO₂NR^(k′)R^(m′) or —OSO₂—(C₁-C₄)-alkyl, or R^(a′) and R^(b′)     together are a (C₃-C₄)-alkylene bridge which may be substituted by     halogen or (C₁-C₄)-alkyl, or a (C₃-C₄)-alkenylene bridge which may     be substituted by halogen or (C₁-C₄)-alkyl, or a C₄-alkadienylene     bridge which may be substituted by halogen or (C₁-C₄)-alkyl, and -   R^(g′) and R^(h′) independently of one another are hydrogen,     halogen, (C₁-C₄)-alkyl, trifluoromethyl, methoxy, methylthio or     —COOR^(l′), where -   R^(c′) is hydrogen, halogen, (C₁-C₄)-alkyl or methoxy, -   R^(d′) is hydrogen, halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl,     —COOR^(j′) or —CONR^(k′)R^(m′), -   R^(e′) is hydrogen, halogen, (C₁-C₄)-alkyl, —COOR^(j),     trifluoromethyl or methoxy, or R^(d) and R^(e) together are a     (C₃-C₄)-alkylene bridge, -   R^(f′) is hydrogen, halogen or (C₁-C₄)-alkyl, -   R^(X′) and R^(Y′) independently of one another are hydrogen,     halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylthio,     trifluoromethyl, nitro or cyano, -   R^(j′), R^(k′) and R^(m′) independently of one another are hydrogen     or (C₁-C₄)-alkyl, -   R^(k′) and R^(m′) together are a C₄-C₆-alkylene bridge or a     (C₄-C₆)-alkylene bridge which is interrupted by oxygen, NH or     —N((C₁-C₄)-alkyl)-, and -   R^(n′) is (C₁-C₄)-alkyl, phenyl or phenyl which is substituted by     halogen, (C₁-C₄)-alkyl, methoxy, nitro or trifluoromethyl, -   preferably     -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,     -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,     -   1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,     -   1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, -   g) compounds of the type of the acylsulfamoylbenzamides of the     formula (S-IX), known from EP-A-1019368, if appropriate also in salt     form,

in which

-   R¹⁰¹ is methyl, methoxy or trifluoromethoxy; -   R¹⁰² is hydrogen, chlorine or methyl; -   R¹⁰³ is hydrogen, ethyl or propargyl; -   R¹⁰⁴ is ethyl, cyclopropyl, isopropyl or propargyl,     -   or -   R¹⁰³ and R¹⁰⁴ together form the group (CH₂)₄, -   including the stereoisomers, and the salts customary in agriculture.

Preference is given to herbicide-safener combinations comprising (A) a herbicidally effective amount of one or more compounds of the formula (I) or salts thereof and (B) an amount, acting as an antidote, of one or more safeners.

Herbicidally effective amount in the sense of the invention is an amount of one or more herbicides sufficient to have an adverse impact on plant growth. In the sense of the invention, an amount which acts as an antidote is an amount of one or more safeners sufficient to reduce the phytotoxic action of crop protection agents (for example herbicides) in crop plants.

The compounds of the formula (S-II) are known, for example, from EP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (U.S. Pat. No. 4,891,057), EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0 346 620 (WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA 94/7120) and the literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula (S-III) are known from EP-A-0 086 750, EP-A-0 94349 (U.S. Pat. No. 4,902,340), EP-A-0 191736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366 and the literature cited therein or can be prepared by or analogously to the processes described therein. Furthermore, some compounds are described in EP-A-0 582 198 and WO 2002/34048.

The compounds of the formula (S-IV) are known from numerous patent applications, for example U.S. Pat. Nos. 4,021,224 and 4,021,229.

Compounds of the group B (b) are furthermore known from CN-A-87/102 789, EP-A-365484 and from “The Pesticide Manual”, The British Crop Protection Council and the Royal Society of Chemistry, 11th edition, Farnham 1997.

The compounds of the group B (c) are described in WO-A-97/45016, those of group B (d) in WO-A-99/16744, those of group B (e) in EP-A-365484 and those of group B (g) in EP-A-1019368.

The publications cited contain detailed statements about preparation processes and starting materials and mention preferred compounds. These publications are expressly referred to; by reference, they form part of the present description.

Preference is given to herbicide-safener combinations comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

-   R²⁴ is hydrogen, (C₁-C₁₈)-alkyl, (C₃-C₁₂)-cycloalkyl,     (C₂-C₈)-alkenyl and (C₂-C₁₈)-alkynyl, where the carbon-containing     groups may be substituted by one or more, preferably up to three,     radicals R⁵⁰; -   R⁵⁰ is identical or different and is halogen, hydroxyl,     (C₁-C₈)-alkoxy, (C₁-C₈)-alkylthio, (C₂-C₈)-alkenylthio,     (C₂-C₈)-alkynylthio, (C₂-C₈)-alkenyloxy, (C₂-C₈)-alkynyloxy,     (C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkoxy, cyano, mono- and     di(C₁-C₄)-alkylamino, carboxyl, (C₁-C₈)-alkoxycarbonyl,     (C₂-C₈)-alkenyloxycarbonyl, (C₁-C₈)-alkylthiocarbonyl,     (C₂-C₈)-alkynyloxycarbonyl, (C₁-C₈)-alkylcarbonyl,     (C₂-C₈)-alkenylcarbonyl, (C₂-C₈)-alkynylcarbonyl,     1-(hydroxyimino)-(C₁-C₆)-alkyl,     1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkoxyimino]-(C₁-C₆)-alkyl, (C₁-C₈)-alkylcarbonylamino,     (C₂-C₈)-alkenylcarbonylamino, (C₂-C₈)-alkynylcarbonylamino,     aminocarbonyl, (C₁-C₈)-alkylaminocarbonyl,     di-(C₁-C₆)-alkylaminocarbonyl, (C₂-C₆)-alkenylaminocarbonyl,     (C₂-C₆)-alkynylaminocarbonyl, (C₁-C₈)-alkoxycarbonylamino,     (C₁-C₈)-alkylaminocarbonylamino, (C₁-C₆)-alkylcarbonyloxy which is     unsubstituted or substituted by R⁵¹, (C₂-C₆)-alkenylcarbonyloxy,     (C₂-C₆)-alkynylcarbonyloxy, (C₁-C₈)-alkylsulfonyl, phenyl,     phenyl-(C₁-C₆)-alkoxy, phenyl-(C₁-C₆)-alkoxycarbonyl, phenoxy,     phenoxy-(C₁-C₆)-alkoxy, phenoxy-(C₁-C₆)-alkoxycarbonyl,     phenylcarbonyloxy, phenylcarbonylamino,     phenyl-(C₁-C₆)-alkylcarbonylamino, where the phenyl ring of the 9     last-mentioned radicals is unsubstituted or mono- or     polysubstituted, preferably up to trisubstituted, by radicals R⁵²;     SiR′₃, —O—SiR′₃, R′₃Si—(C₁-C₈)-alkoxy, —CO—O—NR′₂, —O—N═CR′₂,     —N═CR′₂, —O—NR′₂, —NR′₂, CH(OR′)₂, —O—(CH₂)_(m)—CH(OR)₂,     —CR′″(OR′)₂, —O—(CH₂)_(m)CR′″(OR′)₂ or by     R″O—CHR′″CHCOR″—(C₁-C₆)-alkoxy, -   R⁵¹ is identical or different and is halogen, nitro, (C₁-C₄)-alkoxy     and phenyl which is unsubstituted or substituted by one or more,     preferably up to three, radicals R⁵²; -   R⁵² is identical or different and is halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy or nitro; -   R′ is identical or different and is hydrogen, (C₁-C₄)-alkyl, phenyl     which is unsubstituted or substituted by one or more, preferably up     to three, radicals R⁵², or two radicals R′ together form a     (C₂-C₆)-alkanediyl chain; -   R″ is identical or different and is (C₁-C₄)-alkyl, or two radicals     R″ together form a (C₂-C₆)-alkanediyl chain; -   R′″ is hydrogen or (C₁-C₄)-alkyl; -   m is 0, 1, 2, 3, 4, 5 or 6.

Particular preference is given to herbicide-safener combinations according to the invention comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

-   R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, where the     carbon-containing radicals above are unsubstituted or mono- or     polysubstituted by halogen or mono- or disubstituted, preferably     monosubstituted, by radicals R⁵⁰, R⁵⁰ are identical or different and     are hydroxyl, (C₁-C₄)-alkoxy, carboxyl, (C₁-C₄)-alkoxycarbonyl,     (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-alkynyloxycarbonyl,     1-(hydroxyimino)-(C₁-C₄)-alkyl, 1[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl     and 1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl; —SiR′₃, —O—N═CR′₂,     —N═CR′₂, —NR′₂ and —O—NR′₂, in which R′ is identical or different     and is hydrogen, (C₁-C₄)-alkyl or, as a pair, is a     (C₄-C₅)-alkanediyl chain, -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which     is unsubstituted or substituted by one or more radicals from the     group consisting of halogen, cyano, nitro, amino, mono- and     di-[(C₁-C₄)-alkyl]amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio and     (C₁-C₄)-alkylsulfonyl; -   R^(x′) is hydrogen or COOR²⁴, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₇)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl, -   R¹⁷, R¹⁹ are identical or different and are halogen, methyl, ethyl,     methoxy, ethoxy, (C₁-C₂)-haloalkyl, preferably hydrogen, halogen or     (C₁-C₂)-haloalkyl.

Very particular preference is given to safeners in which the symbols and indices in the formula (S-II) are as defined below:

-   R¹⁷ is halogen, nitro or (C₁-C₄)-haloalkyl; -   n′ is 0, 1, 2 or 3; -   R¹⁸ is a radical of the formula OR²⁴, -   R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, where the     carbon-containing radicals above are unsubstituted or mono- or     polysubstituted, preferably up to trisubstituted, by identical or     different halogen radicals or up to disubstituted, preferably     monosubstituted, by identical or different radicals from the group     consisting of hydroxyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl,     (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-alkynyloxycarbonyl,     1-(hydroxyimino)-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl and radicals of the formulae     —SiR′₃, —O—N═R′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, where the radicals R′     in the formulae mentioned are identical or different and are     hydrogen, (C₁-C₄)-alkyl or, as a pair, are (C₄-C₅)-alkanediyl; -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which     is unsubstituted or substituted by one or more radicals from the     group consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,     (C₁-C₄)-haloalkyl and (C₁-C₄)-haloalkoxy, and -   R^(x′) is hydrogen or COOR²⁶, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₇)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl.

Very particular preference is also given to safeness of the formula (S-III) in which the symbols and indices are as defined below:

-   R¹⁹ is halogen or (C₁-C₄)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁹)_(n′) is preferably 5-Cl; -   R²⁰ is a radical of the formula OR²⁴; -   T is CH₂ or CH(COO—((C₁-C₃)-alkyl)) and -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl or     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, preferably hydrogen or (C₁-C₈)-alkyl.

Especially preferred are safeners of the formula (II) in which the symbols and indices are as defined below:

-   W is (W1); -   R¹⁷ is halogen or (C₁-C₂)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-C₁₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl; -   R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl or     (C₃-C₇)-cycloalkyl, preferably hydrogen or (C₁-C₄)-alkyl, and -   R^(x′) is COOR²⁶, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₄)-haloalkyl, (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     hydrogen or (C₁-C₄)-alkyl.

Also especially preferred are herbicidal compositions comprising a safener of the formula (S-II) in which the symbols and indices are as defined below:

-   W is (W2); -   R¹⁷ is halogen or (C₁-C2)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-C₁₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     ((C₁-C₄)-alkoxy)-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl; and -   R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₃-C₇)-cycloalkyl or unsubstituted or substituted phenyl,     preferably hydrogen, (C₁-C₄)-alkyl or phenyl which is unsubstituted     or substituted by one or more radicals from the group consisting of     halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, nitro, cyano and     (C₁-C₄)-alkoxy.

Especially preferred are also safeners of the formula (II) in which the symbols and indices are as defined below:

-   W is (W3); -   R¹⁷ is halogen or (C₁-C₂)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-C₁₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl, and -   R²⁸ is (C₁-C₈)-alkyl or (C₁-C₄)-haloalkyl, preferably C₁-haloalkyl.

Especially preferred are also safeners of the formula (S-II) in which the symbols and indices are as defined below:

-   W is (W4); -   R¹⁷ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₂)-haloalkyl, preferably     CF₃, or (C₁-C₄)-alkoxy; -   n′ is 0, 1, 2 or 3; -   m′ is 0 or 1; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₄)-alkyl, carboxy-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₄)-alkyl, preferably     (C₁-C₄)-alkoxy-CO—CH₂, (C₁-C₄)-alkoxy-CO—C(CH₃)H—, HO—CO—CH₂— or     HO—CO—C(CH₃)H, and -   R²⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₃-C₇)-cycloalkyl or phenyl which is unsubstituted or substituted     by one or more radicals from the group consisting of halogen,     (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, nitro, cyano and (C₁-C₄)-alkoxy.

Particularly suitable safeners for the herbicidally active compounds of the formula (I) are the following groups of compounds:

-   a) compounds of the type of the     dichlorophenylpyrazoline-3-carboxylic acid (i.e. of the formula     (S-II) in which W═(W1) and (R¹⁷)_(n′)=2,4-Cl₂), preferably compounds     such as ethyl     1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate     (S-II-1, mefenpyr-diethyl), mefenpyr-dimethyl and mefenpyr (S-1′-0),     and related compounds as described in WO-A 91/07874; -   b) derivatives of dichlorophenylpyrazolecarboxylic acid (i.e. of the     formula (S-II) in which W=(W2) and (R¹⁷)_(n′)=2,4-Cl₂), preferably     compounds such as ethyl     1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S-II-2),     ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate     (S-II-3), ethyl     1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate     (S-II-4), ethyl     1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S-II-5) and     related compounds, as described in EP-A-0 333 131 and EP-A-0 269     806; -   c) compounds of the type of the triazolecarboxylic acids (i.e. of     the formula (S-II) in which W=(W3) and (R¹⁷)_(n′)=2,4-Cl₂),     preferably compounds such as fenchlorazole-ethyl, i.e. ethyl     1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate     (S-II-6), and related compounds (see EP-A-0 174 562 and EP-A-0 346     620); -   d) compounds of the type of the 5-benzyl- or     5-phenyl-2-isoxazoline-3-carboxylic acid or of the     5,5-diphenyl-2-isoxazoline-3-carboxylic acid, such as isoxadifen     (S-II-12), (in which W=(W4)), preferably compounds such as ethyl     5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S-II-7) or ethyl     5-phenyl-2-isoxazoline-3-carboxylate (S-II-8) and related compounds,     as described in WO-A-91/08202, or of ethyl     5,5-diphenyl-2-isoxazolinecarboxylate (S-II-9, isoxadifen-ethyl) or     n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S-II-10) or of ethyl     5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S-II-11),     as described in WO-A-95/07897. -   e) Compounds of the type of the 8-quinolineoxyacetic acid, for     example those of the formula (S-III) in which (R¹⁹)_(n′)=5-Cl,     R²⁰=OR²⁴ and T=CH₂, preferably the compounds     -   1-methylhexyl (5-chloro-8-quinolineoxy)acetate (S-III-1,         cloquintocet-mexyl),     -   1,3-dimethylbut-1-yl (5-chloro-8-quinolineoxy)acetate (S-III-2),     -   4-allyloxybutyl (5-chloro-8-quinolineoxy)acetate (S-III-3),     -   1-allyloxyprop-2-yl(5-chloro-8-quinolineoxy)acetate (S-III-4),     -   ethyl (5-chloro-8-quinolineoxy)acetate (S-III-5),     -   methyl (5-chloro-8-quinolineoxy)acetate (S-III-6),     -   allyl (5-chloro-8-quinolineoxy)acetate (S-III-7),     -   2-(2-propylideneiminoxy)-1-ethyl         (5-chloro-8-quinolineoxy)acetate (S-III-8),     -   2-oxoprop-1-yl(5-chloro-8-quinolineoxy)acetate (S-III-9),     -   (5-chloro-8-quinolineoxy)acetic acid (S-III-10) and its salts,         as described, for example, in WO-A-2002/34048,     -   and related compounds as described in EP-A-0 860 750, EP-A-0 094         349 and EP-A-0 191 736 or EP-A-0 492 366. -   f) Compounds of the type of the (5-chloro-8-quinolineoxy)malonic     acid, i.e. of the formula (S-III) in which (R¹⁹)_(n′)=5-Cl,     R²⁰=OR²⁴, T=—CH(COO-alkyl)-, preferably the compounds diethyl     (5-chloro-8-quinolineoxy)malonate (S-III-11), diallyl     (5-chloro-8-quinolineoxy)-malonate, methyl ethyl     (5-chloro-8-quinolineoxy)malonate and related compounds, as     described in EP-A-0 582 198. -   g) Compounds of the type of the dichloroacetamide, i.e. of the     formula (S-IV), preferably:     -   N,N-diallyl-2,2-dichloroacetamide (dichlormid (S-IV-1), from         U.S. Pat. No. 4,137,070),         4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (IV-2,         benoxacor, from EP 0 149 974),     -   N1,N2-diallyl-N2-dichloroacetylglycinamide (DKA-24 (IV-3), from         HU 2143821),     -   4-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (AD-67),     -   2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide         (PPG-1292),     -   3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148, S-IV-4),     -   3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,     -   3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine,     -   3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine         (furilazole (S-IV-5), MON 13900),     -   1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-one         (dicyclonon, BAS 145138). -   h) Compounds of the group B(b), preferably     -   1,8-naphthalic anhydride (S-b-1),     -   methyl diphenylmethoxyacetate (S-b-2),     -   cyanomethoxyimino(phenyl)acetonitrile (cyometrinil) (S-b-3),     -   1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron)         (S-b-4),     -   O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton)         (S-b-5),     -   4-chlorophenyl methylcarbamate (mephenate) (S-b-6),     -   O,O-diethyl O-phenyl phosphorothioate (dietholate) (S-b-7),     -   4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415,         CAS-Regno: 31541-57-8) (S-b-8),     -   1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil)         (S-b-9),     -   4′-chloro-2,2,2-trifluoroacetophenone         O-1,3-dioxolan-2-ylmethyloxime (fluxofenim) (S-b-10),     -   4,6-dichloro-2-phenylpyrimidine (fenclorim) (S-b-11),     -   benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate         (flurazole) (S-b-12),     -   2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191) (S-b-13),     -   N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron)         (S-b-14),     -   (2,4-dichlorophenoxy)acetic acid (2,4-D),     -   (4-chlorophenoxy)acetic acid,     -   (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),     -   4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),     -   (4-chloro-o-tolyloxy)acetic acid (MCPA),     -   4-(4-chloro-o-tolyloxy)butyric acid,     -   4-(4-chlorophenoxy)butyric acid,     -   3,6-dichloro-2-methoxybenzoic acid (dicamba),     -   1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate         (lactidichlor)     -   and their salts and esters, preferably their (C₁-C₈)-esters.

Preferred safeners are furthermore compounds of the formula (S-V) or salts thereof in which

-   R³⁰ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, furanyl or     thienyl, where each of the 4 last-mentioned radicals is     unsubstituted or substituted by one or more substituents from the     group consisting of halogen, (C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy and     (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also     (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl, -   R³¹ is hydrogen, -   R³² is halogen, halo-(C₁-C₄)-alkyl, halo-(C₁-C₄)-alkoxy,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl, preferably halogen,     (C₁-C₄)-haloalkyl, such as trifluoromethyl, (C₁-C₄)-alkoxy,     halo-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylsulfonyl, -   R³³ is hydrogen, -   R³⁴ is halogen, (C₁-C₄)-alkyl, halo-(C₁-C₄)-alkyl,     halo-(C₁-C₄)-alkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,     cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylcarbonyl, preferably halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-haloalkyl, such as trifluoromethyl, halo-(C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy or (C₁-C₄)-alkylthio, -   n is 0, 1 or 2 and -   m is 1 or 2.

Particular preference is given to compounds of the formula (S-V) in which

-   R³⁰=H₃C—O—CH₂—, R³¹=R³³=H, R³⁴=2-OMe (S-V-1), -   R³⁰=H₃C—O—CH₂—, R³¹=R³³=H, R³⁴=2-OMe-5-Cl (S-V-2), -   R³⁰=cyclopropyl, R³¹=R³³=H, R³⁴=2-OMe (S-V-3), -   R³⁰=cyclopropyl, R³¹=R³³=H, R³⁴=2-OMe-5-Cl (S-V-4), -   R³⁰=cyclopropyl, R³¹=R³³=H, R³⁴=2-Me (S-V-5), -   R³⁰=tert-butyl, R³¹=R³³=H, R³⁴=2-OMe (S-V-6).

Preference is furthermore given to safeners of the formula (S-VI) in which

-   X³ is CH; -   R³⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₂-C₆)-alkenyl,     (C₆-C₆)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl having     up to 3 heteroatoms from the group consisting of nitrogen, oxygen     and sulfur, where the six last-mentioned radicals are optionally     substituted by one or more identical or different substituents from     the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,     (C₁-C₂)-alkylsulfinyl, (C₁-C₂)-alkylsulfonyl, (C₃-C₆)-cycloalkyl,     (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylcarbonyl and phenyl and, in the     case of cyclic radicals, also (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl; -   R³⁶ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl,     where the three last-mentioned radicals are optionally substituted     by one or more identical or different substituents from the group     consisting of halogen, hydroxy, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and     (C₁-C₄)-alkylthio; -   R³⁷ is halogen, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, nitro,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl; -   R³⁸ is hydrogen; -   R³⁹ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,     cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylcarbonyl; -   n is 0, 1 or 2 and -   m is 1 or 2.

Preferred safeners of the formula (S-VII) are (S-3-1), (S-3-2), (S-3-3), (S-3-4) and (S-3-5).

Preferred safeners of the formula (VIII) are

-   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-1), -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea     (S-VIII-2), -   1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-3)     and -   1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea (S-VIII-4),

Preferred safeners of the formula S-IX are compounds of the formulae S-IX-A1 to S-IX-A4,

from among which the compound S-IX-A3 is very particularly preferred as safener.

Particularly preferred combinations of herbicidally active compounds of the formula (I) as listed in any of Tables 1 to 4 and safeners (B) are those in which the safener (B) is selected from the group of safeners consisting of the compounds of the formulae S-II-1 (mefenpyr-diethyl), S-II-9 (isoxadifen-ethyl), S-III-1 (chloquintocet-mexyl), S-b-11 (fenclorim), S-b-14 (dymron), S-IX-A3 (4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide, N-({4-[(cyclopropylamino)carbonyl]phenyl}-sulfonyl)-2-methoxybenzamide, very particularly preferred as safeners (B) are the compounds S-II-1 and S-IX-A3).

Particularly preferred for use in rice is isoxadifen-ethyl. Particularly preferred for use in cereals are mefenpyr-diethyl, cloquintocet-mexyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide], in corn in particular isoxadifen-ethyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)-benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide]. For use in sugar cane, preference is given to isoxadifen-ethyl.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.

Some of the safeners are already known as herbicides and accordingly, in addition to the herbicidal action against harmful plants, also act by protecting the crop plants.

The weight ratios of herbicide (mixture) to safener generally depend on the herbicide application rate and the effectiveness of the safener in question and may vary within wide limits, for example in the range from 200:1 to 1:200, preferably from 100:1 to 1:100, in particular from 20:1 to 1:20. The safeners may be formulated analogously to the compounds of the formula (I) or their mixtures with other herbicides/pesticides and be provided and used as a finished formulation or as a tank mix with the herbicides.

For application, the formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersable granules with water. Preparations in the form of dusts, granules for soil application or granules for broadcasting and sprayable solutions are usually not diluted with other inert substances prior to application.

The required application rate of the compounds of the formula (I) varies according to the external conditions such as, inter alia, temperature, humidity and the type of herbicide used. It may vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance; however, preferably it is between 0.005 and 5 kg/ha.

The present invention is illustrated in more detail by the examples below; however, these examples do not limit the invention in any way.

A. SYNTHESIS EXAMPLES

Some examples of syntheses of compounds of the formula (I) or salts thereof are described in an exemplary manner below.

3-[(S)-{[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 483) and 3-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 664)

3-({[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl}methyl]thio)-5,5-dimethyl-4,5-dihydroisoxazole (3.5 g, 9.741 mmol), which can be obtained according to EP 1 541 561 A, WO 2005/105755 A, WO 2004/014138 A or WO 2007/003295 A, is initially charged in 80 ml of toluene. With stirring, 3-chloroperbenzoic acid (1.856 g, 8.28 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at room temperature for a further 4 hours. For work-up, the reaction mixture is washed successively with water, aqueous NaHSO₃ solution, aqueous NaHCO₃ solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is triturated with n-heptane, filtered off and dried. The racemic 3-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole obtained (3.0 g, 99% pure) is separated into the enantiomers by preparative chiral HPLC (column: Chiralcel® OD; mobile phase: n-hexane/2-propanol 90:10; flow rate: 0.6 ml/min; column temperature: 25° C.). This gives 1.524 g (41.7% of theory) of 3-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R_(t)=11.124 min) and 1.410 g (38.6% of theory) of 3-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R_(t)=14.244 min).

The absolute configuration of 3-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole was confirmed by X-ray analysis.

3-[(S)-(2,6-Difluorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 6) and 3-[(R)-(2,6-difluorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 228)

Commercially available (−)-2,2′-dihydroxy-1,1′-binaphthyl [(S)-binol], 0.056 g, 0.2 mmol] is initially charged in chlororform (5 ml). The catalyst titanium(IV) isopropoxide (0.03 ml, 0.1 mmol) is then added dropwise, followed by water (0.070 g, 3.9 mmol). The mixture is stirred at room temperature for 15 minutes. 3-[(2,6-Difluorobenzyl)sulfanyl]-5,5-dimethyl-4,5-dihydroisoxazole (0.5 g, 1.9 mmol), which can be obtained according to WO 2001/012613 A, WO 2006/024820 A or WO 2006/037945 A, is then added, followed by the dropwise addition of cumene hydroperoxide (0.43 ml, 80%, 2.2 mmol). The reaction is stirred at room temperature for 6 hours and then allowed to stand overnight. For work-up, the reaction mixture is diluted with chloroform and washed successively with water, twice with 5% strength Na₂S₂O₅ solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is chromatographed on silica gel (heptane/ethyl acetate 10:0 to 7:3). This gives 100 mg (19% of theory) of 3-[(2,6-difluorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole with an ee (R) of 12%. The enantiomer mixture obtained is then separated into the enantiomers by preparative chiral HPLC. This gives 0.03 g (6% of theory) of 3-[(S)-(2,6-difluorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R_(t)=18.293 min) and 0.03 g (6% of theory) of 3-[(R)-(2,6-difluorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R_(t)=35.353 min).

3-[(S)-(2,6-Dichlorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 32) and 3-[(R)-(2,6-dichlorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (Ex. 254)

a) Preparation of 2,6-Dichlorobenzyl Imidothiocarbamate Hydrochloride

2,6-Dichlorobenzyl chloride (19.0 g, 97 mmol) is initially charged in 200 ml of ethanol. Thiourea is added, and the mixture is stirred at reflux for 8 hours. The reaction is concentrated and the solid is triturated with tetrahydrofuran, filtered off with suction and dried. This gives 26.12 g of product (94% of theory). The salt is reacted further without any further reaction steps.

b) Preparation of 3-(2,6-dichlorobenzyl)sulfanyl-5,5-dimethyl-4,5-dihydroisoxazole

2,6-Dichlorobenzyl imidothiocarbamate hydrochloride (1.533 g, 6 mmol) is added to a vigorously stirred mixture consisting of 50 ml of toluene and 50% strength aqueous sodium hydroxide solution (21 g), and the mixture is stirred vigorously for a further 1.5 hours. Tetra-n-butylammonium bromide (0.509 g, 2 mmol) and 5,5-dimethyl-3-(methylsulfonyl)-4,5-dihydroisoxazole (1.0 g, 6 mmol) are then added, and the mixture is stirred vigorously at 25° C. for a further 4 hours. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. This gives 1.50 g of product (87% of theory). NMR (CDCl₃, 400 MHz): 1.44 (s, 6H, CH₃); 2.83 (s, 2H, CH₂); 4.63 (s, 2H, SCH₂); 7.18 (m, 1H, Ar); 7.31 (d, 2H, Ar).

c) Asymmetric Sulfoxidation

The catalyst tungsten(VI) oxide (WO₃; 0.018 g, 0.07 mmol), the ligand (DHQ)₂Pyr (0.134 g, 0.15 mmol) and 3-[(2,6-dichlorobenzyl)sulfanyl]-5,5-dimethyl-4,5-dihydroisoxazole (0.440 g, 1.5 mmol) are initially charged in THF (5 ml). Hydrogen peroxide (H₂O₂ 30%, 0.17 ml, 1.65 mmol) is added dropwise with ice-bath cooling. The mixture is stirred at the same temperature for a further 8 hours and allowed to stand in the fridge (−5° C.) over the weekend. For work-up, the reaction mixture is filtered, added to water and extracted with ethyl acetate. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The crude product contains 3-[(2,6-dichlorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole with an ee (S) of 41% and the corresponding sulfone (0.2 g) and is directly separated into the enantiomeric sulfoxides by preparative chiral HPLC. This gives 0.02 g (4% of theory) of 3-[(S)-(2,6-dichlorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R=19.746 min) and 0.03 g (6% of theory) of 3-[(R)-(2,6-dichlorobenzyl)sulfinyl]-5,5-dimethyl-4,5-dihydroisoxazole (R=32.760 min).

Retention times (R_(t), in Minuten) and enantiomeric excess (ee) of chiral compounds were determined by analytic chiral HPLC [Chiralcel® OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The racemates or enantiomeric mixtures were separated into the respective enantiomers by preparative chiral HPLC [Chiralcel® OD column (250×5 mm, particle size 10 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The compounds described in Tables 1-4 below are obtained according to or analogously to the synthesis examples described above.

In the tables:

-   Me=methyl -   Et=ethyl -   Ph=phenyl -   Pr=n-propyl -   cPr=cyclopropyl -   iPr=isopropyl -   Bu=n-butyl -   cBu=cyclobutyl -   iBu=isobutyl -   sBu=sec-butyl -   tBu=tert-butyl -   cPen=cyclopentyl -   cHex=cyclohexyl

TABLE 1 Compounds of the formula Ia-S (Ia-S)

Ex. No. R¹ R² R³ R⁴ R⁵ 1. H H H H H 2. F H H H H 3. F F H H H 4. F H F H H 5. F H H F H 6. F H H H F 7. H F H F H 8. F Me H H F 9. Ph H H H H 10. OCH₂C≡CH H H H H 11. OS(O)₂Me H H H H 12. F H H H Cl 13. CF₃ H H H H 14. OCHF₂ H H H H 15. S(O)CH₃ H H H H 16. SCF₃ H H H H 17. CN H H H H 18. Me H H H H 19. H OMe H OMe H 20. F H H H CF₃ 21. F CF₃ H H F 22. OCH₂CH₂O H F H 23. S(O)CF₃ H H H H 24. F H C(O)OMe H H 25. F H C(O)OEt H H 26. OCF₃ H H H H 27. OCF₂O H H H 28. OCH₂OCH₂ H H H 29. Br H H H H 30. I H H H H 31. Cl H Cl H H 32. Cl H H H Cl 33. H Cl Cl H H 34. Cl Cl Cl H H 35. Cl Cl H Cl H 36. Cl Cl H H Cl 37. Cl H Cl Cl H 38. Cl H H Cl Cl 39. H Cl Cl Cl H 40. NO₂ H H H H 41. H Cl H H H 42. H H Cl H H 43. Cl Cl H H H 44. Cl H H Cl H 45. H Cl H Cl H 46. C(O)OEt H H H H 47. Me H H H H 48. H OMe H H H 49. H H OMe H H 50. H OEt H H H 51. H OPr H H H 52. H OiPr H H H 53. H OCHF₂ H H H 54. H OCF₃ H H H 55. C(O)OMe H H H H 56. CH₂OMe H H H H 57. F Cl H H H 58. Me H H H Me 59. OEt Me H H H 60. F Me H H H 61. H Me H H H 62. H H Me H H 63. OMe H H H H 64. H H OMe H H 65. H CN H H H 66. H C(O)OMe H H H 67. C(O)OH H H H H 68. H F F H H 69. F H H H NO₂ 70. F H F H F 71. F F H H F 72. Et H H H Et 73. NO₂ C(O)OMe H H H 74. F F F H H 75. F F H F H 76. H F F F H 77. F H F F H 78. Me H Me H H 79. Me H H Me H 80. H Me Me H H 81. F H H CF₃ H 82. F CF₃ H H H 83. F H Br H H 84. S(O)₂CF₃ H H H H 85. Cl H H H H 86. Me Me H H H 87. H Me H Me H 88. Me H H H Et 89. F H H H OEt 90. F H CF₃ H H 91. Me H Me H Me 92. OMe H H NO₂ H 93. F F F F F 94. F H H H OMe 95. OMe H H H OMe 96. OEt H H H OEt 97. Me NO₂ H H H 98. Cl H F H H 99. NO₂ H Cl H H 100. NO₂ H H Me H 101. H CF₃ F H H 102. H F H CF₃ H 103. H CF₃ H CF₃ H 104. CF₃ H H CF₃ H 105. H Br H Br H 106. H NO₂ H NO₂ H 107. Me Me H Me Me 108. F H H H I 109. NH₂ H H H F 110. NH₂ H H H H 111. F H H H Br 112. Br H H H Br 113. F H H H C(O)OMe 114. F H H H NMe₂ 115. F H H H NEt₂ 116. Cl H H H Me 117. Cl H H H OCHF₂ 118. Cl H H H OMe 119. Cl H H H OEt 120. Cl H H H OPr 121. Cl H H H OiPr 122. Cl H H H OCH₂CF₃ 123. OBu H H H H 124. F H H H OBu 125. F H H H OPr 126. F H H H OiPr 127. Cl H H H OiBu 128. F H H H OCHF₂ 129. Cl H H H OBu 130. F H H H OCH₂C≡CH 131. OCH₂C(O)OMe H H H H 132. OCH₂C(O)OEt H H H H 133. O(CH₂)₂OMe H H H H 134. O(CH₂)₂OEt H H H H 135. Me H H H OMe 136. Me iPr H H OMe 137. OEt H H H CF₃ 138. CH₂OEt H H H H 139. OC(O)Me H H H H 140. OCH₂Ph H H H H 141. OCH₂CH═CH₂ H H H H 142. Cl H H H OCH₂CH═CH₂ 143. Cl H H H OCH₂C≡CH 144. C(O)OPr H H H H 145. C(O)OiPr H H H H 146. C(O)OBu H H H H 147. C(O)OsBu H H H H 148. C(O)OiBu H H H H 149. C(O)OCH₂CH═CH₂ H H H H 150. C(O)OCH₂C≡CH H H H H 151. C(O)OcPen H H H H 152. OEt H H H Me 153. OPr H H H Me 154. OBu H H H Me 155. Me H H H OCH₂CH═CH₂ 156. Me H H H OCH₂C≡CH 157. OCH₂cPr H H H H 158. OcPen H H H H 159. OcHex H H H H 160. C(O)OCH₂Ph H H H H 161. C(O)OCH₂Ph(2-Cl) H H H H 162. C(O)OCH₂Ph(3-Cl) H H H H 163. C(O)OCH₂Ph(4-Cl) H H H H 164. CH₂OBu H H H H 165. Me Me H H Me 166. Cl H H H C(O)OMe 167. Cl H H H C(O)OEt 168. Cl H H H C(O)OPr 169. Cl H H H C(O)OiPr 170. Cl H H H C(O)OBu 171. Cl H H H C(O)OsBu 172. Cl H H H C(O)OiBu 173. Cl H H H C(O)OCH₂Ph 174. Cl H H H C(O)OCH₂Ph(2-Cl) 175. Cl H H H C(O)OCH₂Ph(3-Cl) 176. Cl H H H C(O)OCH₂Ph(4-Cl) 177. Cl H H OMe H 178. Cl H H OEt H 179. Cl H H OPr H 180. Cl H H OiPr H 181. Cl H H OBu H 182. Cl H H OCH₂CH═CH₂ H 183. Cl H H OCH₂C≡CH H 184. Et H H H OMe 185. Cl H H H C(O)OH 186. F H H H C(O)OH 187. F H H H C(O)OEt 188. F H H H C(O)OPr 189. F H H H C(O)OiPr 190. F H H H C(O)OBu 191. F H H H C(O)OsBu 192. F H H H C(O)OiBu 193. F H H H C(O)OCH₂Ph 194. F H H H C(O)OCH₂Ph(2-Cl) 195. F H H H C(O)OCH₂Ph(3-Cl) 196. F H H H C(O)OCH₂Ph(4-Cl) 197. OEt H H H Et 198. OPr H H H Et 199. OiPr H H H Et 200. OCH₂CH═CH₂ H H H Et 201. OCH₂C≡CH H H H Et 202. F F H F F 203. C(O)OMe Me H H H 204. C(O)OEt Me H H H 205. C(O)OiBu Me H H H 206. Me H H Me OMe 207. Me H H Me OEt 208. Me H H Me OPr 209. F Me H H Cl 210. Cl H H F H 211. F H H F Cl 212. F H H Cl H 213. Cl H H CF₃ H 214. Cl Me H H H 215. F H H OMe H 216. F H H CF₃ H 217. Cl H OCH₂O H 218. F H H Me Cl 219. OMe H H Cl H 220. Me H H F H 221. OMe H H OMe H 222. H OCF₂O H H

TABLE 2 Compounds of the formula Ia-R (Ia-R)

Ex. No. R¹ R² R³ R⁴ R⁵ 223. H H H H H 224. F H H H H 225. F F H H H 226. F H F H H 227. F H H F H 228. F H H H F 229. H F H F H 230. F Me H H F 231. Ph H H H H 232. OCH₂C≡CH H H H H 233. OS(O)₂Me H H H H 234. F H H H Cl 235. CF₃ H H H H 236. OCHF₂ H H H H 237. S(O)CH₃ H H H H 238. SCF₃ H H H H 239. CN H H H H 240. Me H H H H 241. H OMe H OMe H 242. F H H H CF₃ 243. F CF₃ H H F 244. OCH₂CH₂O H F H 245. S(O)CF₃ H H H H 246. F H C(O)OMe H H 247. F H C(O)OEt H H 248. OCF₃ H H H H 249. OCF₂O H H H 250. OCH₂OCH₂ H H H 251. Br H H H H 252. I H H H H 253. Cl H Cl H H 254. Cl H H H Cl 255. H Cl Cl H H 256. Cl Cl Cl H H 257. Cl Cl H Cl H 258. Cl Cl H H Cl 259. Cl H Cl Cl H 260. Cl H H Cl Cl 261. H Cl Cl Cl H 262. NO₂ H H H H 263. H Cl H H H 264. H H Cl H H 265. Cl Cl H H H 266. Cl H H Cl H 267. H Cl H Cl H 268. C(O)OEt H H H H 269. Me H H H H 270. H OMe H H H 271. H H OMe H H 272. H OEt H H H 273. H OPr H H H 274. H OiPr H H H 275. H OCHF₂ H H H 276. H OCF₃ H H H 277. C(O)OMe H H H H 278. CH₂OMe H H H H 279. F Cl H H H 280. Me H H H Me 281. OEt Me H H H 282. F Me H H H 283. H Me H H H 284. H H Me H H 285. OMe H H H H 286. H H OMe H H 287. H CN H H H 288. H C(O)OMe H H H 289. C(O)OH H H H H 290. H F F H H 291. F H H H NO₂ 292. F H F H F 293. F F H H F 294. Et H H H Et 295. NO₂ C(O)OMe H H H 296. F F F H H 297. F F H F H 298. H F F F H 299. F H F F H 300. Me H Me H H 301. Me H H Me H 302. H Me Me H H 303. F H H CF₃ H 304. F CF₃ H H H 305. F H Br H H 306. S(O)₂CF₃ H H H H 307. I H H H H 308. Me Me H H H 309. H Me H Me H 310. H OMe H OMe H 311. Me H H H Et 312. F H H H OEt 313. F H CF₃ H H 314. Me H Me H Me 315. OMe H H NO₂ H 316. F F F F F 317. F H H H OMe 318. OMe H H H OMe 319. OEt H H H OEt 320. Me NO₂ H H H 321. Cl H F H H 322. NO₂ H Cl H H 323. NO₂ H H Me H 324. H CF₃ F H H 325. H F H CF₃ H 326. H CF₃ H CF₃ H 327. CF₃ H H CF₃ H 328. H Br H Br H 329. H NO₂ H NO₂ H 330. Me Me H Me Me 331. F H H H I 332. NH₂ H H H F 333. F Me H H F 334. NH₂ H H H H 335. F H H H Br 336. Br H H H Br 337. F H H H C(O)OMe 338. F H H H NMe₂ 339. F H H H NEt₂ 340. Cl H H H Me 341. Cl H H H OCHF₂ 342. Cl H H H OMe 343. Cl H H H OEt 344. Cl H H H OPr 345. Cl H H H OiPr 346. Cl H H H OCH₂CF₃ 347. OBu H H H H 348. F H H H OBu 349. F H H H OPr 350. F H H H OiPr 351. Cl H H H OiBu 352. F H H H OCHF₂ 353. Cl H H H OBu 354. F H H H OCH₂C≡CH 355. OCH₂C(O)OMe H H H H 356. OCH₂C(O)OEt H H H H 357. O(CH₂)₂OMe H H H H 358. O(CH₂)₂OEt H H H H 359. Me H H H OMe 360. Me iPr H H OMe 361. OEt H H H CF₃ 362. CH₂OEt H H H H 363. OC(O)Me H H H H 364. OCH₂Ph H H H H 365. OCH₂CH═CH₂ H H H H 366. Cl H H H OCH₂CH═CH₂ 367. Cl H H H OCH₂C≡CH 368. C(O)OPr H H H H 369. C(O)OiPr H H H H 370. C(O)OBu H H H H 371. C(O)OsBu H H H H 372. C(O)OiBu H H H H 373. C(O)OCH₂CH═CH₂ H H H H 374. C(O)OCH₂C≡CH H H H H 375. C(O)OcPen H H H H 376. OEt H H H Me 377. OPr H H H Me 378. OBu H H H Me 379. Me H H H OCH₂CH═CH₂ 380. Me H H H OCH₂C≡CH 381. OCH₂cPr H H H H 382. OcPen H H H H 383. OcHex H H H H 384. C(O)OCH₂Ph H H H H 385. C(O)OCH₂Ph(2-Cl) H H H H 386. C(O)OCH₂Ph(3-Cl) H H H H 387. C(O)OCH₂Ph(4-Cl) H H H H 388. CH₂OBu H H H H 389. Me Me H H Me 390. Cl H H H C(O)OMe 391. Cl H H H C(O)OEt 392. Cl H H H C(O)OPr 393. Cl H H H C(O)OiPr 394. Cl H H H C(O)OBu 395. Cl H H H C(O)OsBu 396. Cl H H H C(O)OiBu 397. Cl H H H C(O)OCH₂Ph 398. Cl H H H C(O)OCH₂Ph(2-Cl) 399. Cl H H H C(O)OCH₂Ph(3-Cl) 400. Cl H H H C(O)OCH₂Ph(4-Cl) 401. Cl H H OMe H 402. Cl H H OEt H 403. Cl H H OPr H 404. Cl H H OiPr H 405. Cl H H OBu H 406. Cl H H OCH₂CH═CH₂ H 407. Cl H H OCH₂C≡CH H 408. Et H H H OMe 409. Cl H H H C(O)OH 410. F H H H C(O)OH 411. F H H H C(O)OEt 412. F H H H C(O)OPr 413. F H H H C(O)OiPr 414. F H H H C(O)OBu 415. F H H H C(O)OsBu 416. F H H H C(O)OiBu 417. F H H H C(O)OCH₂Ph 418. F H H H C(O)OCH₂Ph(2-Cl) 419. F H H H C(O)OCH₂Ph(3-Cl) 420. F H H H C(O)OCH₂Ph(4-Cl) 421. OEt H H H Et 422. OPr H H H Et 423. OiPr H H H Et 424. OCH₂CH═CH₂ H H H Et 425. OCH₂C≡CH H H H Et 426. F F H F F 427. C(O)OMe Me H H H 428. C(O)OEt Me H H H 429. C(O)OiBu Me H H H 430. Me H H Me OMe 431. Me H H Me OEt 432. Me H H Me OPr 433. F Me H H Cl 434. Cl H H F H 435. F H H F Cl 436. F H H Cl H 437. Cl H H CF₃ H 438. Cl Me H H H 439. F H H OMe H 440. F H H CF₃ H 441. Cl H OCH₂O H 442. F H H Me Cl 443. OMe H H Cl H 444. Me H H F H 445. OMe H H OMe H 446. H OCF₂O H H

TABLE 3 Compounds of the formula Ib-S (Ib-S)

Ex. No. R⁶ R⁷ R⁸ 447. CF₃ Ph Cl 448. Ph Me Cl 449. CF₃ Ph SO₂Me 450. CF₃ Ph NMe₂ 451. CF₃ tBu Cl 452. CF₃ H Cl 453. CF₃ CHF₂ Cl 454. Cl CHF₂ CF₃ 455. OEt Me CF₃ 456. CF₃ Me OMe 457. CF₃ Me OPh(2-Cl) 458. CF₃ Me OcPen 459. CF₃ Me CN 460. Cl Et Cl 461. CHF₂ Me Cl 462. CF₃ —(CH₂)₃O— 463. CF₃ H Cl 464. H Me Cl 465. Me Me Me 466. Me Me Cl 467. Cl Me Cl 468. CF₃ Me Cl 469. Cl Me CF₃ 470. CF₃ Me F 471. CF₃ Me OH 472. OMe Me CF₃ 473. CF₃ Me OEt 474. CF₃ Me OiPr 475. CF₃ Me OPr 476. CF₃ Me OtBu 477. CF₃ Me OBu 478. CF₃ Me OcHex 479. CF₃ Me OCH₂cPr 480. CF₃ Me OCH₂cPen 481. CF₃ Me OCH₂cHex 482. CF₃ Me OCH₂C≡CH 483. CF₃ Me OCHF₂ 484. OCHF₂ Me CF₃ 485. CF₃ Me OCH₂CHF₂ 486. CF₃ Me OCH₂CF₃ 487. CF₃ Me OCH₂CN 488. CF₃ Me OCH₂Ph 489. CF₃ Me OPh 490. CF₃ Me OPh(3-Cl) 491. CF₃ Me OPh(3-OMe) 492. CF₃ Me OPh(4-Cl) 493. CF₃ Me OPh(4-Me) 494. CF₃ Me OPh(4-OMe) 495. CF₃ Me OC(O)Me 496. CF₃ Me SO₂Me 497. CF₃ Me SEt 498. CF₃ Me SO₂Et 499. CF₃ Me SO₂Ph 500. CF₃ Me Me 501. CF₃ Me Et 502. CF₃ Et Cl 503. Cl Et CF₃ 504. CF₃ iPr Cl 505. Cl iPr CF₃ 506. CF₃ Pr Cl 507. Cl Pr CF₃ 508. CF₃ tBu Cl 509. Cl tBu CF₃ 510. CF₃ sBu Cl 511. Cl sBu CF₃ 512. CF₃ iBu Cl 513. Cl iBu CF₃ 514. CF₃ Bu Cl 515. Cl Bu CF₃ 516. CF₃ CH₂Ph Cl 517. Cl CH₂Ph CF₃ 518. CF₃ cPen Cl 519. Cl cPen CF₃ 520. CF₃ cHex Cl 521. CF₃ CH₂cPr Cl 522. Cl CH₂cPr CF₃ 523. CF₃ CHMecPr Cl 524. Cl CHMecPr CF₃ 525. CF₃ CH₂cPr(2-Me) Cl 526. Cl CH₂cPr(2-Me) CF₃ 527. CF₃ CH₂cBu Cl 528. Cl CH₂cBu CF₃ 529. CF₃ CH₂cPen Cl 530. Cl CH₂cPen CF₃ 531. CF₃ CH₂cHex Cl 532. Cl CH₂cHex CF₃ 533. CF₃ CH₂CH═CH₂ Cl 534. Cl CH₂CH═CH₂ CF₃ 535. CF₃ CH₂C≡CH Cl 536. Cl CH₂C≡CH CF₃ 537. CF₃ CHMeC≡CH Cl 538. Cl CHMeC≡CH CF₃ 539. CF₃ CH₂C≡CMe Cl 540. Cl CH₂C≡CMe CF₃ 541. CF₃ CHF₂ OMe 542. OMe CHF₂ CF₃ 543. CF₃ CH₂CF₃ Cl 544. Cl CH₂CF₃ CF₃ 545. CF₃ CH₂OMe Cl 546. Cl CH₂OMe CF₃ 547. CF₃ CH₂OEt Cl 548. Cl CH₂OEt CF₃ 549. CF₃ CH₂CH₂OH Cl 550. Cl CH₂CH₂OH CF₃ 551. CF₃ CH₂CH₂OMe Cl 552. Cl CH₂CH₂OMe CF₃ 553. CF₃ CH₂CH₂OEt Cl 554. Cl CH₂CH₂OEt CF₃ 555. CF₃ CH₂SMe Cl 556. Cl CH₂SMe CF₃ 557. CF₃ CH₂SO₂Me Cl 558. Cl CH₂SO₂Me CF₃ 559. CF₃ CH₂CN Cl 560. Cl CH₂CN CF₃ 561. CF₃ CH₂C(O)OEt Cl 562. Cl CH₂C(O)OEt CF₃ 563. CF₃ CH₂C(O)NH₂ Cl 564. Cl CH₂C(O)NH₂ CF₃ 565. CF₃ CH₂C(O)NMe₂ Cl 566. Cl CH₂C(O)NMe₂ CF₃ 567. CF₃ CH₂C(O)Me Cl 568. Cl CH₂C(O)Me CF₃ 569. CF₃ CH₂CH₂C(O)Me Cl 570. Me Ph Me 571. Me Ph Cl 572. Et Ph Cl 573. Pr Ph Cl 574. iPr Ph Cl 575. tBu Ph Cl 576. CF₃ Ph H 577. CF₃ Ph Me 578. CF₃ Ph CF₃ 579. CF₃ Ph F 580. CF₃ Ph OMe 581. CF₃ Ph OEt 582. CF₃ Ph OiPr 583. CF₃ Ph OPr 584. CF₃ Ph OtBu 585. CF₃ Ph OCHF₂ 586. CF₃ Ph SO₂Me 587. CF₃ Ph CN 588. CF₃ Ph(2-Cl) Cl 589. CF₃ Ph(3-Cl) Cl 590. CF₃ Ph(4-Cl) Cl 591. CF₃ Ph(4-F) Cl 592. CF₃ Ph(4-OMe) Cl 593. CF₃ Ph(4-Me) Cl 594. CF₃ Ph(4-NO₂) Cl 595. CF₃ Ph(4-CN) Cl 596. CF₃ Ph(4-C(O)Me) Cl 597. CF₃ Ph(4-C(O)OMe) Cl 598. CF₃ pyrimidinyl-2-yl Cl 599. CF₃ 4,6- Cl dimethoxypyrimi- dinyl-2-yl 600. CF₃ SO₂Me Cl 601. CF₃ SO₂Ph Cl 602. CF₃ C(O)Me Cl 603. CF₃ C(O)Ph Cl 604. CF₃ C(O)OMe Cl 605. CF₃ tBu OMe 606. Me Me OCH₂CF₃ 607. CF₃ Me

608. CF₃ Me H 609. CF₃ Me SO₂iPr 610. CF₃ Me CF₃ 611. CF₃ Me CHF₂ 612. CHF₂ Me CF₃ 613. CF₂CF₃ Me CF₃ 614. CF₃ Me CF₂CF₃ 615. CF₃ Me OCH₂CH₂OMe 616. CF₃ Me OCH₂CH₂CH₂F 617. CF₃ Me OCH(CH₂F)₂ 618. CF₃ Me OCH₂CF₂CHF₂ 619. CF₃ Me OCH₂CF═CH₂ 620. CF₃ Me OCH(Me)CF₃ 621. CF₃ Me OCH(Me)CH₂F 622. CF₃ Me OCH₂CHF₂ 623. OCH₂CF₃ Me CF₃ 624. OCH₂CF₃ Me CHF₂ 625. CHF₂ Me CHF₂ 626. CHF₂ Me OCH₂CF₃ 627. CHF₂ Me OCHF₂

TABLE 4 Compounds of the formula Ib-R (Ib-R)

Ex. No. R⁶ R⁷ R⁸ 628. CF₃ Ph Cl 629. Ph Me Cl 630. CF₃ Ph SO₂Me 631. CF₃ Ph NMe₂ 632. CF₃ tBu Cl 633. CF₃ H Cl 634. CF₃ CHF₂ Cl 635. Cl CHF₂ CF₃ 636. OEt Me CF₃ 637. CF₃ Me OMe 638. CF₃ Me OPh(2-Cl) 639. CF₃ Me OcPen 640. CF₃ Me CN 641. Cl Et Cl 642. CHF₂ Me Cl 643. CF₃ —(CH₂)₃O— 644. CF₃ H Cl 645. H Me Cl 646. Me Me Me 647. Me Me Cl 648. Cl Me Cl 649. CF₃ Me Cl 650. Cl Me CF₃ 651. CF₃ Me F 652. CF₃ Me OH 653. OMe Me CF₃ 654. CF₃ Me OEt 655. CF₃ Me OiPr 656. CF₃ Me OPr 657. CF₃ Me OtBu 658. CF₃ Me OBu 659. CF₃ Me OcHex 660. CF₃ Me OCH₂cPr 661. CF₃ Me OCH₂cPen 662. CF₃ Me OCH₂cHex 663. CF₃ Me OCH₂C≡CH 664. CF₃ Me OCHF₂ 665. OCHF₂ Me CF₃ 666. CF₃ Me OCH₂CHF₂ 667. CF₃ Me OCH₂CF₃ 668. CF₃ Me OCH₂CN 669. CF₃ Me OCH₂Ph 670. CF₃ Me OPh 671. CF₃ Me OPh(3-Cl) 672. CF₃ Me OPh(3-OMe) 673. CF₃ Me OPh(4-Cl) 674. CF₃ Me OPh(4-Me) 675. CF₃ Me OPh(4-OMe) 676. CF₃ Me OC(O)Me 677. CF₃ Me SO₂Me 678. CF₃ Me SEt 679. CF₃ Me SO₂Et 680. CF₃ Me SO₂Ph 681. CF₃ Me Me 682. CF₃ Me Et 683. CF₃ Et Cl 684. Cl Et CF₃ 685. CF₃ iPr Cl 686. Cl iPr CF₃ 687. CF₃ Pr Cl 688. Cl Pr CF₃ 689. CF₃ tBu Cl 690. Cl tBu CF₃ 691. CF₃ sBu Cl 692. Cl sBu CF₃ 693. CF₃ iBu Cl 694. Cl iBu CF₃ 695. CF₃ Bu Cl 696. Cl Bu CF₃ 697. CF₃ CH₂Ph Cl 698. Cl CH₂Ph CF₃ 699. CF₃ cPen Cl 700. Cl cPen CF₃ 701. CF₃ cHex Cl 702. CF₃ CH₂cPr Cl 703. Cl CH₂cPr CF₃ 704. CF₃ CHMecPr Cl 705. Cl CHMecPr CF₃ 706. CF₃ CH₂cPr(2-Me) Cl 707. Cl CH₂cPr(2-Me) CF₃ 708. CF₃ CH₂cBu Cl 709. Cl CH₂cBu CF₃ 710. CF₃ CH₂cPen Cl 711. Cl CH₂cPen CF₃ 712. CF₃ CH₂cHex Cl 713. Cl CH₂cHex CF₃ 714. CF₃ CH₂CH═CH₂ Cl 715. Cl CH₂CH═CH₂ CF₃ 716. CF₃ CH₂C≡CH Cl 717. Cl CH₂C≡CH CF₃ 718. CF₃ CHMeC≡CH Cl 719. Cl CHMeC≡CH CF₃ 720. CF₃ CH₂C≡CMe Cl 721. Cl CH₂C≡CMe CF₃ 722. CF₃ CHF₂ OMe 723. OMe CHF₂ CF₃ 724. CF₃ CH₂CF₃ Cl 725. Cl CH₂CF₃ CF₃ 726. CF₃ CH₂OMe Cl 727. Cl CH₂OMe CF₃ 728. CF₃ CH₂OEt Cl 729. Cl CH₂OEt CF₃ 730. CF₃ CH₂CH₂OH Cl 731. Cl CH₂CH₂OH CF₃ 732. CF₃ CH₂CH₂OMe Cl 733. Cl CH₂CH₂OMe CF₃ 734. CF₃ CH₂CH₂OEt Cl 735. Cl CH₂CH₂OEt CF₃ 736. CF₃ CH₂SMe Cl 737. Cl CH₂SMe CF₃ 738. CF₃ CH₂SO₂Me Cl 739. Cl CH₂SO₂Me CF₃ 740. CF₃ CH₂CN Cl 741. Cl CH₂CN CF₃ 742. CF₃ CH₂C(O)OEt Cl 743. Cl CH₂C(O)OEt CF₃ 744. CF₃ CH₂C(O)NH₂ Cl 745. Cl CH₂C(O)NH₂ CF₃ 746. CF₃ CH₂C(O)NMe₂ Cl 747. Cl CH₂C(O)NMe₂ CF₃ 748. CF₃ CH₂C(O)Me Cl 749. Cl CH₂C(O)Me CF₃ 750. CF₃ CH₂CH₂C(O)Me Cl 751. Me Ph Me 752. Me Ph Cl 753. Et Ph Cl 754. Pr Ph Cl 755. iPr Ph Cl 756. tBu Ph Cl 757. CF₃ Ph H 758. CF₃ Ph Me 759. CF₃ Ph CF₃ 760. CF₃ Ph F 761. CF₃ Ph OMe 762. CF₃ Ph OEt 763. CF₃ Ph OiPr 764. CF₃ Ph OPr 765. CF₃ Ph OtBu 766. CF₃ Ph OCHF₂ 767. CF₃ Ph SO₂Me 768. CF₃ Ph CN 769. CF₃ Ph(2-Cl) Cl 770. CF₃ Ph(3-Cl) Cl 771. CF₃ Ph(4-Cl) Cl 772. CF₃ Ph(4-F) Cl 773. CF₃ Ph(4-OMe) Cl 774. CF₃ Ph(4-Me) Cl 775. CF₃ Ph(4-NO₂) Cl 776. CF₃ Ph(4-CN) Cl 777. CF₃ Ph(4-C(O)Me) Cl 778. CF₃ Ph(4-C(O)OMe) Cl 779. CF₃ pyrimidinyl-2-yl Cl 780. CF₃ 4,6- Cl dimethoxypyrimi- dinyl-2-yl 781. CF₃ SO₂Me Cl 782. CF₃ SO₂Ph Cl 783. CF₃ C(O)Me Cl 784. CF₃ C(O)Ph Cl 785. CF₃ C(O)OMe Cl 786. CF₃ tBu OMe 787. Me Me OCH₂CF₃ 788. CF₃ Me

789. CF₃ Me H 790. CF₃ Me SO₂iPr 791. CF₃ Me CF₃ 792. CF₃ Me CHF₂ 793. CHF₂ Me CF₃ 794. CF₂CF₃ Me CF₃ 795. CF₃ Me CF₂CF₃ 796. CF₃ Me OCH₂CH₂OMe 797. CF₃ Me OCH₂CH₂CH₂F 798. CF₃ Me OCH(CH₂F)₂ 799. CF₃ Me OCH₂CF₂CHF₂ 800. CF₃ Me OCH₂CF═CH₂ 801. CF₃ Me OCH(Me)CF₃ 802. CF₃ Me OCH(Me)CH₂F 803. CF₃ Me OCH₂CHF₂ 804. OCH₂CF₃ Me CF₃ 805. OCH₂CF₃ Me CHF₂ 806. CHF₂ Me CHF₂ 807. CHF₂ Me OCH₂CF₃ 808. CHF₂ Me OCHF₂

Retention times (R_(t), in minutes) of selected compounds of Tables 1-4 of chiral compounds were determined by analytic chiral HPLC [Chiralcel® OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

TABLE 5 Compounds of the formula Ia-S

(Ia-S) Ex. No. R¹ R² R³ R⁴ R⁵ Physical data 6 F H H H F [α]_(D) = +218.3° R_(t) = 18.293 min 12 F H H H Cl R_(t) = 18.729 min 32 Cl H H H Cl [α]_(D) = +136.3° R_(t) = 19.746 min

TABLE 6 Compounds of the formula Ia-R

(Ia-R) Ex. No. R¹ R² R³ R⁴ R⁵ Physical data 228 F H H H F [α]_(D) = −212.2° R_(t) = 35.353 min 234 F H H H Cl R_(t) = 34.250 min 254 Cl H H H Cl [α]_(D) = −127.9° R_(t) = 32.760 min

TABLE 7 Compounds of the formula Ib-S

(Ib-S) Ex. No. R⁶ R⁷ R⁸ Physical data 483 CF₃ Me OCHF₂ [α]_(D) = −70.7° R_(t) = 11.124 min 610 CF₃ Me CF₃ [α]_(D) = −30.2° *R_(t) = 4.658 min *hexane/2-propanol 80:20 v/v.

TABLE 8 Compounds of the formula Ib-R

(Ib-R) Ex. No. R⁶ R⁷ R⁸ Physical data 664 CF₃ Me OCHF₂ [α]_(D) = +63.4° R_(t) = 14.244 min 791 CF₃ Me CF₃ [α]_(D) = +27.3° *R_(t) = 5.490 min *hexane/2-propanol 80:20 v/v.

In addition, NMR data for racemates comprising compounds of the formula (I) according to the invention were generated. Hereinbelow, to distinguish them from the stereochemically pure compounds of the formula (I), the racemates are referred to as compounds of the formula (Ia) and of the formula (Ib), respectively.

NMR data were measured at 400 MHz and in the solvent CDCl₃. The chemical shift δ is stated in ppm (TMS reference).

Compounds of the formula (Ia) (racemates)

Ex. No. R¹ R² R³ R⁴ R⁵  6/228 F H H H F 12/234 F H H H Cl 32/254 Cl H H H Cl

NMR Compound 6/228 (CDCl₃, 400 MHz, δ in ppm):

1.47 (s, 3H, CH₃); 1.49 (s, 3H, CH₃); 3.07 (d, 1H, CH₂); 3.22 (d, 1H, CH₂); 4.36 (d, 1H, S(O)CH₂); 4.40 (d, 1H, S(O)CH₂); 6.95 (m, 2H, Ar); 7.31 (m, 1H, Ar).

NMR Compound 12/234 (CDCl₃, 400 MHz, δ in ppm):

1.47 (s, 3H, CH₃); 1.51 (s, 3H, CH₃); 3.13 (d, 1H, CH₂); 3.25 (d, 1H, CH₂); 4.48 (d, 1H, S(O)CH₂); 4.54 (d, 1H, S(O)CH₂); 7.04 (m, 1H, Ar); 7.28 (m, 2H, Ar).

NMR Compound 32/254 (CDCl₃, 400 MHz, δ in ppm):

1.47 (s, 3H, CH₃); 1.53 (s, 3H, CH₃); 3.21 (d, 1H, CH₂); 3.27 (d, 1H, CH₂); 4.69 (br s, 2H, S(O)CH₂); 7.23 (t, 1H, Ar); 7.37 (d, 2H, Ar).

Compounds of the formula (Ib) (racemates)

Ex. No. R⁶ R⁷ R⁸ 483/664 CF₃ Me OCHF₂ 610/791 CF₃ Me CF₃

NMR Compound 483/664 (CDCl₃, 400 MHz):

1.50 (s, 3H, CH₃); 1.52 (s, 3H, CH₃); 3.04 (d, 1H, CH₂); 3.17 (d, 1H, CH₂); 3.84 (s, 3H, NCH₃); 4.15 (br s, 2H, S(O)CH₂); 6.94 (dd, 1H, OCHF₂).

NMR Compound 610/791 (CDCl₃, 400 MHz, δ in ppm):

1.47 (s, 3H, CH₃); 1.52 (s, 3H, CH₃); 3.04 (d, 1H, CH₂); 3.20 (d, 1H, CH₂); 4.09 (s, 3H); 4.30 (d, 1H, S(O)CH₂); 4.39 (d, 1H, S(O)CH₂).

B. FORMULATION EXAMPLES

-   a) A dust is obtained by mixing 10 parts by weight of a compound of     the formula (I) and 90 parts by weight of talc as inert substance     and comminuting the mixture in a hammer mill. -   b) A wettable powder which is readily dispersible in water is     obtained by mixing 25 parts by weight of a compound of the formula     (I), 64 parts by weight of kaolin-containing quartz as inert     substance, 10 parts by weight of potassium lignosulfonate and 1 part     by weight of sodium oleoylmethyltaurate as wetting agent and     dispersant, and grinding the mixture in a pinned-disk mill. -   c) A readily water-dispersible dispersion concentrate is obtained by     mixing 20 parts by weight of a compound of the formula (I) with 6     parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3     parts by weight of isotridecanol polyglycol ether (8 EO) and 71     parts by weight of paraffinic mineral oil (boiling range for example     about 255 to above 277° C.) and grinding the mixture in a ball mill     to a fineness of below 5 microns. -   d) An emulsifiable concentrate is obtained from 15 parts by weight     of a compound of the formula (I), 75 parts by weight of     cyclohexanone as solvent and 10 parts by weight of oxethylated     nonylphenol as emulsifier. -   e) Water-dispersible granules are obtained by mixing     -   75 parts by weight of a compound of the formula (I)     -   10 parts by weight of calcium lignosulfonate,     -   5 parts by weight of sodium lauryl sulfate,     -   3 parts by weight of polyvinyl alcohol and     -   7 parts by weight kaolin     -   grinding the mixture in a pinned-disk mill, and granulating the         powder in a fluidized bed by spraying on water as granulating         liquid. -   f) Water-dispersible granules are also obtained by homogenizing and     precomminuting     -   25 parts by weight of a compound of the formula (I),     -   5 parts by weight of sodium         2,2′-dinaphthylmethane-6,6′-disulfonate,     -   2 parts by weight of sodium oleoylmethyltaurate,     -   1 part by weight of polyvinyl alcohol,     -   17 parts by weight calcium carbonate and     -   50 parts by weight of water     -   in a colloid mill, then grinding the mixture in a bead mill, and         atomizing and drying the resulting suspension in a spray tower,         using a single-fluid nozzle.

C. BIOLOGICAL EXAMPLES

1. Pre-emergence herbicidal effect and crop plant compatibility

-   -   Seeds of monocotyledonous or dicotyledonous weed plants or crop         plants are planted in wood-fiber pots in sandy loam and covered         with soil. The compounds according to the invention, formulated         in the form of wettable powders (WP), are then applied as         aqueous suspension at a water application rate of 600 l/ha         (converted) with the addition of 0.2% of wetting agent to the         surface of the covering soil.     -   After the treatment, the pots are placed in a greenhouse and         kept under good growth conditions for the test plants. After         about 3 weeks, the effect of the preparations is scored visually         in comparison with untreated controls (herbicidal effect in         percent (%): 100% activity=the plants have died, 0%         activity=like control plants).     -   As shown by the results, the compounds according to the         invention have good herbicidal pre-emergence activity against a         broad spectrum of weed grasses and broad-leaved weeds. The         compounds according to Examples 6, 32, 228, 254, 483, 664, 610,         791 and other compounds from Tables 1-4, for example, have very         good herbicidal activity against harmful plants such as, for         example, Avena fatua, Stellaria media, Echinochloa crus-galli,         Lolium multiflorum, Setaria viridis, Amaranthus retroflexus,         Viola tricolor, Veronica persica and Alopecurus myosuroides when         applied by the pre-emergence method at an application rate of         0.32 kg and less of active substance per hectare.     -   In addition, some substances also spare monocotyledonous and         dicotyledonous crops such as corn and oilseed rape. Some of the         compounds according to the invention have high selectivity and         are therefore suitable for controlling unwanted vegetation in         agricultural crops by the pre-emergence method.

The following results were achieved with the compounds of the formula (Ia) by the pre-emergence method:

Com- Application pound rate BRSNW ALOMY LOLMU SETVI 6 320 g of active 0 100 100 100 (S config.) compound/ha 80 g of active 0 90 80 60 compound/ha Racemate 320 g of active 30 100 80 40 of 6 compound/ha (S config.) 80 g of active 20 70 80 40 and 228 compound/ha (R config.) 228 (R 320 g of active 0 80 0 50 config.) compound/ha 80 g of active 0 60 0 0 compound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (Ia) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop compatibility of the (S) stereoisomers in oilseed rape is surprisingly high. In addition, the crop compatibility of the compound of the formula (Ia) having the (R) configuration is better than that of the racemate. With potent herbicidal activity, the (S) stereoisomer has better crop compatibility (selectivity) in the crop plant winter rape (SETVI). At an active compound application rate of 80 g of ai/ha, there is a marked difference in the activity S>rac>R.

The following results were achieved with the compounds of the formula (Ib) by the pre-emergence method:

Com- Application pound rate BRSNW ALOMY LOLMU SETVI 483 (S 80 g of active 0 100 100 90 config.) compound/ha 20 g of active 0 80 60 80 compound/ha Racemate 80 g of active 0 90 90 80 of 483 compound/ha (S config.) 20 g of active 0 0 0 40 and 664 compound/ha (R config.)

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (Ib) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. This is true in particular for the application rate of 20 g of active compound/ha.

At the same time, the crop compatibility of the (S) stereoisomers in oilseed rape is surprisingly high. It is particularly surprising that, at increased herbicidal activity, the crop compatibility can be maintained at a constant good level. Usually, crop compatibility (selectivity) decreases with improved herbicidal activity.

The following results were achieved with the compounds of the formula (Ib) by the pre-emergence method:

Application Compound rate ZEAMX ALOMY POLCO VERPE 32 (S 80 g of active 0 100 80 100 config.) compound/ha 20 g of active 0 80 40 40 compound/ha Racemate 80 g of active 10 90 20 — of 32 (S compound/ha config.) and 20 g of active 0 80 — 0 254 compound/ha (R config.) 254 80 g of active 0 60 20 20 (R config.) compound/ha 20 g of active 0 0 10 0 compound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (Ib) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture.

At the same time, the crop compatibility of the (S) stereoisomers in corn (ZEAMX) is surprisingly high.

Abbreviations

-   ALOMY Alopecurus myosuroides (black-grass) -   LOLMU: Lolium multiflorum (Italian ryegrass) -   SETVI: Setaria viridis (green foxtail) -   BRSNW: Brassica napus (winter rape) -   ZEAMX: Zea mays (corn)     2. Post-Emergence Herbicidal Effect and Crop Plant Compatibility     -   Seeds of monocotyledonous and dicotyledonous weed and crop         plants are placed in sandy loam in wood fibre pots, covered with         soil and cultivated in a greenhouse under good growth         conditions. 2 to 3 weeks after sowing, the test plants are         treated at the one-leaf stage. The compounds according to the         invention, formulated in the form of wettable powders (WP), are         then applied by spraying as aqueous suspension at a water         application rate of 600 l/ha (converted) with the addition of         0.2% of wetting agent to the green parts of the plants. After         the test plants have been kept in the greenhouse under optimum         growth conditions for about 3 weeks, the activity of the         preparations is rated visually in comparison to untreated         controls (herbicidal activity in percent (%): 100% activity=the         plants have died, 0% activity=like control plants).     -   As shown by the results, the compounds according to the         invention have good herbicidal post-emergence activity against a         plurality of weed grasses and broad-leaved weeds. The compounds         Nos. 6, 32, 228, 254, 483, 664, 610 and 791 and other compounds         from Tables 1-4, for example, have very good herbicidal activity         against harmful plants such as, for example, Avena fatua,         Echinochloa crus-galli, Lolium multiflorum, Setaria viridis and         Alopecurus myosuroides when applied by the post-emergence method         at an application rate of 0.32 kg and less of active substance         per hectare.     -   In addition, some substances also spare monocotyledonous and         dicotyledonous crops such as corn and oilseed rape. Some of the         compounds according to the invention have high selectivity and         are therefore suitable for controlling unwanted vegetation in         agricultural crops by the post-emergence method. 

The invention claimed is:
 1. An optically active compound of the formula (I) in the form of its (S) stereoisomer and/or an agrochemically acceptable salt and/or an agrochemically acceptable quaternized nitrogen derivative thereof

wherein Y is

and the individual substituents R¹ to R⁵ are each independently of one another selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH, formyl, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy, (C₁-C₆)-haloalkylcarbonyloxy, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl, (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-halo-alkoxycarbonyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkenylcarbonyl, (C₂-C₆)-haloalkenylcarbonyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-haloalkenyloxycarbonyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₂-C₆)-alkynylcarbonyl, (C₂-C₆)-haloalkynylcarbonyl, (C₂-C₆)-alkynyloxy, (C₂-C₆)-haloalkynyloxy, (C₂-C₆)-alkynyloxycarbonyl, (C₂-C₆)-haloalkynyloxycarbonyl, (C₁-C₆)-alkylthiocarbonyl, (C₁-C₆)-haloalkylthiocarbonyl, (C₁-C₆)-alkylthiocarbonyloxy, (C₁-C₆)-haloalkylthiocarbonyloxy, (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy, (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy, (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl, (C₆-C₁₄)-aryloxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl,(C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy, (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkylcarbonyloxy, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy, (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-haloalkylsulfonyl, (C₁-C₆)-haloalkylthio, (C₁-C₆)-haloalkylsulfinyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkylsulfonyloxy, (C₄-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio, (C₆-C₁₄)-arylsulfinyl, mono-((C₁-C₆)-alkyl)-amino, mono-((C₁-C₆)-haloalkyl)-amino, di-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-haloalkyl)-amino, ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)-amino, N-((C₁-C₆)-alkanoyl)-amino, N-((C₁-C₆)-haloalkanoyl)-amino, aminocarbonyl-(C₁-C₆)-alkyl, mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl, mono-((C₁-C₆)-alkyl)-aminocarbonyl, di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkylcarbonyloxy, (C₃-C₈)-cycloalkoxycarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyloxy, (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkenylcarbonyl, (C₃-C₈)-cycloalkenyloxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkenylcarbonyloxy, (C₃-C₈)-cycloalkenyloxycarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy, (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio, (C₃-C₈)-cycloalkenylthio, (C₃-C₆)-alkynylthio, hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl, 3-oxetanyloxy, pyrimidinyl-2-yl and 4,6-dimethoxypyrimidinyl-2-yl, C(O)NR⁹R¹⁰ where R⁹ and R¹⁰ independently of one another are hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups, where the radicals mentioned may, if appropriate, be attached cyclically to one another, provided they are ortho to one another and/or two substituents ortho to one another together form a (C₁-C₆)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C₁-C₆)-alkylene group may be mono-or polysubstituted by halogen and the halogen substituents in question may be identical or different; and where the radicals cycloalkyl and aryl may be mono-or polysubstituted independently of one another.
 2. The compound of the formula (I) as claimed in claim 1 wherein the substituents R¹ to R⁵ are independently of one another selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy, (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino, C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl, (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups; and/or two substituents ortho to one another together form a (C₁-C₆)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C₁-C₆)-alkylene group may be mono-or polysubstituted by halogen and the halogen substituents in question may be identical or different where the radicals cycloalkyl and aryl may be mono-or polysubstituted independently of one another.
 3. A process for preparing a compound of formula (I) as claimed in claim 1, which comprises oxidizing a thioether of formula (II)

with one equivalent of an oxidizing agent to give a sulfoxide of formula (I)


4. The process as claimed in claim 3 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium metaperiodate, organic peroxides and organic peracids.
 5. A composition comprising at least one compound of the formula (I) as claimed in claim
 1. 6. The composition as claimed in claim 5 wherein the composition comprises at least one further active compound selected from the group consisting of a further herbicide and at least one safener.
 7. A compound of the formula (I) as claimed in claim 1 that is capable of acting as plant growth regulator.
 8. A composition as claimed in claim 6 that is capable of acting as a plant growth regulator.
 9. The composition as claimed in claim 6 that is capable of controlling plants in specific plant crops and/or as plant protection regulator.
 10. A compound wherein (Ia-S)

wherein R¹ R² R³ R⁴ R⁵ F H H H F F H H H Cl Cl H H H  Cl.


11. A composition comprising at least one compound as claimed in claim
 10. 12. The composition as claimed in claim 11 wherein the composition comprises at least one further active compound selected from the group consisting of a further herbicide and at least one safener.
 13. A compound of claim 10, wherein R¹ is F, R² is H, R³ is H, R⁴ is H, and R⁵ is F.
 14. A compound of claim 10, wherein R¹ is Cl, R² is H, R³ is H, R⁴ is H, and R⁵ is Cl.
 15. A method of killing undesired plants, comprising applying the compound of claim 1 to the soil before germination of said undesired plants.
 16. A method of killing undesired plants, comprising applying the compound of claim 1 to post-emergence green parts of said undesired plants. 